Polyolefin adhesive compositions and articles made therefrom

ABSTRACT

Embodiments of the present invention relate to article comprising 1) a functionalized component, 2) tackifier, and 3) an olefin polymer comprising one or more C3 to C40 olefins, optionally one or more diolefins, and less than 5 mole % of ethylene having a Dot T-Peel of 1 Newton or more, a branching index (g′) of 0.95 or less measured at the Mz of the polymer; and an Mw of 100,000 or less; where the functional component is selected from the group consisting of functionalized polymers, functionalized oligomers and beta nucleating agents; and where the Gardner color of the adhesive does not change by more than 7 Gardner units when the adhesive has been heat aged at 180° C. for 48 hours as compared to the Gardner color of the unaged composition.

This application is a continuation of U.S. Ser. No. 10/825,348, filedApr. 15, 2004 now U.S. Pat. No. 7,700,707 which is acontinuation-in-part of U.S. Ser. No. 10/686,951, filed Oct. 15, 2003now U.S. Pat. No. 7,524,910 which claims priority from U.S. Ser. No.60/418,482, filed Oct. 15, 2002 and U.S. Ser. No. 60/460,714, filed Apr.4, 2003 which is also a continuation-in-part of U.S. Ser. No.10/687,508, filed Oct. 15, 2003 now U.S. Pat. No. 7,294,681 which claimspriority from U.S. Ser. No. 60/418,482, filed Oct. 15, 2002 and U.S.Ser. No. 60/460,714, filed Apr. 4, 2003.

This application is related to: 1) U.S. Ser. No. 60/199,093 filed onApr. 21, 2000, 2) U.S. Ser. No. 60/171,715 filed Dec. 21, 1999, 3) U.S.Ser. No. 09/745,394 filed Dec. 21, 2000, 4) U.S. Ser. No. 09/746,332filed Dec. 21, 2000, and 5) WO 01/81493 published Nov. 1, 2001.

FIELD OF THE INVENTION

This invention relates to adhesives comprising: 1) functionalizedcomponent 2) olefin polymers of C₃₋₄₀ olefins having a Dot T-Peel of 1Newton or more, a branching index (g′) of 0.95 or less measured at thez-average molecular weight (Mz) of the polymer, a weight averagemolecular weight (Mw) of 100,000 or less or a branching index (g′) of0.98 or less measured at the z-average molecular weight (Mz) of thepolymer, a weight average molecular weight (Mw) of 30,000 or less, wherethe functionalized component is selected from the group consisting offunctionalized components, functionalized oligomers and beta nucleatingagents; and where the Gardner color of the adhesive does not change bymore than 7 Gardner units when the adhesive has been heat aged at 180°C. for 48 hours as compared to the Gardner color of the unagedcomposition.

BACKGROUND OF THE INVENTION

There is a need in the art for adhesives that are heat stable and low incolor. This invention provides such an adhesive, particular one thatprovides high and low temperature performance.

SUMMARY OF THE INVENTION

This invention relates to adhesives comprising 1) functionalizedcomponent and 2) an olefin polymer comprising one or more C3 to C40olefins where the olefin polymer has:

-   -   a) a Dot T-Peel of 1 Newton or more on Kraft paper; a branching        index (g′) of 0.95 or less measured at the Mz of the polymer; a        Mw of 10,000 to 100,000; and

-   a heat of fusion of 1 to 70 J/g;

-   where the functional component is selected from the group consisting    of functionalized polymers, functionalized oligomers and beta    nucleating agents; and    where the Gardner color of the adhesive does not change by more than    7 Gardner units when the adhesive has been heat aged at 180° C. for    48 hours as compared to the Gardner color of the unaged composition.

This invention relates to adhesives comprising 1) functionalizedcomponent and 2) an olefin polymer comprising one or more C3 to C40olefins where the olefin polymer has:

-   -   a) a Dot T-Peel of 1 Newton or more on Kraft paper;    -   b) a branching index (g′) of 0.98 or less measured at the Mz of        the polymer;    -   c) a Mw of 10,000 to 60,000;    -   d) a heat of fusion of 1 to 50 J/g;        where the functional component is selected from the group        consisting of functionalized polymers, functionalized oligomers        and beta nucleating agents; and where the Gardner color of the        adhesive does not change by more than 7 Gardner units when the        adhesive has been heat aged at 180° C. for 48 hours as compared        to the Gardner color of the unaged composition.

DETAILED DESCRIPTION

By “functionalized polymer” is meant that the polymer is contacted witha functional group, and optionally a catalyst, heat, initiator, or freeradical source to cause all or part of the functional group toincorporate, graft, bond to, physically attach to, and or chemicallyattach to the polymer. In addition, “functionalized component” is alsodefined to include polymer directly polymerized from monomers (or usinginitiatior having a functional group) where the polymer has a functionalgroup at a chain end.

By “functionalized oligomer” is meant that the oligomer is contactedwith a functional group, and optionally a catalyst, heat, initiator, orfree radical source to cause all or part of the functional group toincorporate, graft, bond to, physically attach to, and or chemicallyattach to the oligomer. In addition, “functionalized oligomer” is alsodefined to include polymer directly oligomerized from monomers (or usinginitiatior having a functional group) where the oligomer has afunctional group at a chain end.

By “functional group” is meant any compound with a weight averagemolecular weight of 1000 or less that contains a heteroatom and or anunsaturation. Preferably the functional group is a compound containing aheteroatom, such as maleic anhydride. Preferred functional groupsinclude organic acids, organic amides, organic amines, organic esters,organic anhydrides, organic alcohols, organic acid halides (such as acidchlorides, acid bromides, etc.) organic peroxides, and salts thereof.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-40 mer units and the term polymer refers tocompositions having 41 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the monomer(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

For purposes of this invention, beta nucleating agents are defined to bematerials that cause at least 5% beta crystallization of thecrystallization that occurs (Kvalue of 0.05 or more) in the compositionas measured by the following procedure:

Determination of beta-form crystal content by X-ray method:

A sample of the adhesive is subjected to X-ray diffraction and a K valueis obtained by the following equation:Kvalue=(Hb1) divided by (Hb1+Ha1,+Ha2+Ha3),where:

-   Hb1 is a reflection intensity (height) on (300) plane of beta-form    crystal;-   Ha1 is a reflection intensity (height) on (110) plane of alpha-form    crystal;-   Ha2 is a reflection intensity (height) on (040) plane of alpha-form    crystal; and-   Ha3 is a reflection intensity (height) on (130) plane of alpha-form    crystal.

In a preferred embodiment the adhesives prepared herein have a Kvalue of0.05 or more, preferably 0.10 or more, preferably 0.15 or more,preferably 0.20 or more, preferably 0.25 or more, preferably 0.30 ormore, preferably 0.35 or more, preferably 0.40 or more, preferably 0.45or more, preferably 0.50 or more, preferably 0.55 or more, preferably0.60 or more, preferably 0.65 or more, preferably 0.70 or more,preferably 0.75 or more, preferably 0.80 or more, preferably 0.85 ormore, preferably 0.90 or more, preferably 0.95 or more, preferably 1.0.

For the purposes of this invention and the claims thereto and for easeof reference when a polymer is referred to as comprising an olefin, theolefin present in the polymer is the polymerized form of the olefin. Forease of reference amorphous polypropylene is abbreviated aPP, isotacticpolypropylene is abbreviated iPP, syndiotactic polypropylene isabbreviated sPP, semi-crystalline polypropylene is abbreviated scPP, and“-g-” indicates that the components are grafted.

In a preferred embodiment the functionalized component is present at0.005 to 99 weight %, preferably 0.01 weight % to 99 weight %,preferably 0.05 to 90 weight %, preferably between 0.1 and 75 weight %,more preferably between 0.5 and 60 weight %, more preferably between 1and 50%, more preferably between 1.5 and 40 weight %, more preferablybetween 2 and 30%, more preferably between 2 and 20 weight %, morepreferably between 2 and 15%, more preferably between 2 and 10%, morepreferably between 2 and 5%, based upon the weight of the blend.Preferably the functionalized component is present at 0.005 to 10 weight%, more preferably 0.01 to 10 weight %, based upon the weight of theblend.

In a preferred embodiment, the C3 to C40 Olefin polymer is present inthe adhesive blend at 1 to 99.005 weight %, preferably 1 weight % to99.09 weight %, preferably 10 to 99.05 weight %, preferably between 25and 99.9 weight %, more preferably between 40 and 99.5 weight %, morepreferably between 50 and 99 weight %, more preferably between 60 and98.5 weight %, more preferably between 70 and 98 wt %, more preferablybetween 80 and 98 weight %, more preferably between 85 and 98 wt %, morepreferably between 90 and 98 wt %, more preferably between 95 and 98%,based upon the weight of the blend.

In a preferred embodiment, this invention relates to adhesivescomprising 1) functionalized component and 2) a homopolypropylene or acopolymer of propylene and up to 5 mole % ethylene having:

-   -   a) an isotactic run length of 1 to 30 (isotactic run length        “IRL” is defined to be the percent of mmmm pentad divided by        0.5× percent of mmmr pentad) as determined by Carbon 13 NMR,        preferably 3 to 25, more preferably 4 to 20,    -   b) a percent of r dyad of greater than 20%, preferably from 20        to 70% as determined by Carbon 13 NMR, and    -   c) a heat of fusion of 70 J/g or less, preferably 60 J/g or        less, more preferably between 1 and 55 J/g, more preferably        between 4 and 50 J/g.

In another embodiment this invention relates to adhesives comprising 1)functionalized component and 2) an olefin polymer comprising one or moreC3 to C40 olefins, preferably propylene, and, in some embodiments, lessthan 15 mole % of ethylene (preferably less than 5 mole % ethylene),having:

-   -   a) a Dot T-Peel between 1 Newton and the 10,000 Newtons on kraft        paper;    -   b) a Mz/Mn of 2 to 200; and    -   c) an Mw of X and a g′ of Y (measured at the Mz of the polymer)        according to the following Table C:

TABLE C X (Mw) Y (g′) 100,000 or less, preferably 80,000 or less,preferably 70,000 or 0.9 or less, less, more preferably 60,000 or less,more preferably 50,000 or preferably 0.7 or less less, more preferably40,000 or less, more preferably 30,000 or Preferably less, morepreferably 20,000 or less, more preferably 10,000 or between 0.5-0.9less. In some embodiments X is also at least 7000, more preferably10,000, more preferably at least 15,000. 75,000 or less, preferably70,000 or less, more preferably 0.92 or less, 60,000 or less, morepreferably 50,000 or less, more preferably preferably, 0.6 or 40,000 orless, more preferably 30,000 or less, more preferably less 20,000 orless, more preferably 10,000 or less. In some preferably embodiments Ais also at least 1000, preferably at least 2000, between more preferablyat least 3000, more preferably at least 4000, 0.4-0.6- more preferablyat least 5000, more preferably at least 7000, more preferably 10,000,more preferably at least 15,000. 50,000 or less, more preferably 40,000or less, more preferably 0.95 or less, 30,000 or less, more preferably20,000 or less, more preferably preferably 0.7 or 10,000 or less. Insome embodiments A is also at least 1000, less preferably at least 2000,more preferably at least 3000, more preferably preferably at least 4000,more preferably at least 5000, more between preferably at least 7000,more preferably 10,000, more 0.5-0.7- preferably at least 15,000. 30,000or less, preferably 25,000 or less, more preferably 0.98 or less 20,000or less, more preferably 15,000 or less, more preferably preferably10,000 or less. In some embodiments A is also at least 1000, between0.7-0.98 preferably at least 2000, more preferably at least 3000, morepreferably at least 4000, more preferably at least 5000, more preferablyat least 7000, more preferably 10,000, more preferably at least 15,000.C3 to C40 Olefin Polymers

Preferred olefin polymers (also called “POA's” or “POA polymers”) usefulin this invention are those described in U.S. Ser. No. 10/686,951, filedOct. 15, 2003 and U.S. Ser. No. 10/687,508, filed Oct. 15, 2003, whichare incorporated by reference herein. In particular, pages 23 to 91 ofU.S. Ser. No. 10/686,951 and pages 22 to 168 of U.S. Ser. No. 10/687,508provide specific instruction on how to produce the olefin polymersuseful herein. In general preferred POA's comprise a polypropyleneprepared utilizing two or more catalysts (typically metallocenecatalysts), wherein one catalyst is selected as being capable ofproducing essentially atactic polypropylene (aPP), and the othermetallocene catalyst is selected as being capable of producing isotacticpolypropylene (iPP) under the polymerization conditions utilized.Preferably, under the polymerization conditions utilized, incorporationof aPP and iPP polymer chains may occur within the in-reactor blend suchthat an amount of amorphous polypropylene present in the POA polymer isgrafted to isotactic polypropylene, represented herein as (aPP-g-IPP)and/or such that an amount of isotactic polypropylene present in the POApolymer is grafted to amorphous polypropylene, represented herein as(iPP-g-aPP).

In another embodiment, when Mw of the POA is between 15,000 and 100,000,then the g′<(10⁻¹² Mw²-10⁻⁶ Mw+1.0178).

In a some embodiments the g′ of the POA is 0.9 or less, 0.8 or less, 0.7or less, 0.6 or less, measured at the Mz of the polymer.

In another embodiment the POA has a peak melting point (Tm) between 40and 250° C., or between 60 and 190° C., or between about 60 and 150° C.,or between 80 and 130° C. In some embodiments the peak melting point isbetween 60 and 160° C. In other embodiments the peak melting point isbetween 124-140° C. In other embodiments the peak melting temperature isbetween 40-130° C.

In another embodiment the POA has a viscosity (also referred to aBrookfield Viscosity or Melt Viscosity) of 90,000 mPa·sec or less at190° C. (as measured by ASTM D 3236 at 190° C.; ASTM=American Societyfor Testing and Materials); or 80,000 or less, or 70,000 or less, or60,000 or less, or 50,000 or less, or 40,000 or less, or 30,000 or less,or 20,000 or less, or 10,000 or less, or 8,000 or less, or 5000 or less,or 4000 or less, or 3000 or less, or 1500 or less, or between 250 and6000 mPa·sec, or between 500 and 5500 mPa·sec, or between 500 and 3000mPa·sec, or between 500 and 1500 mPa·sec, and/or a viscosity of 8000mPa·sec or less at 160° C. (as measured by ASTM D 3236 at 160° C.); or7000 or less, or 6000 or less, or 5000 or less, or 4000 or less, or 3000or less, or 1500 or less, or between 250 and 6000 mPa·sec, or between500 and 5500 mPa·sec, or between 500 and 3000 mPa·sec, or between 500and 1500 mPa·sec. In other embodiments the viscosity is 200,000 mPa·secor less at 190° C., depending on the application. In other embodimentsthe viscosity is 50,000 mPa·sec or less depending on the applications.

In another embodiment the POA has a heat of fusion of 70 J/g or less, or60 J/g or less, or 50 J/g or less; or 40 J/g or less, or 30 J/g or less,or 20 J/g or less and greater than zero, or greater than 1 J/g, orgreater than 10 J/g, or between 20 and 50 J/g.

In another embodiment the POA also has a Shore A Hardness (as measuredby ASTM 2240) of 95 or less, 70 or less, or 60 or less, or 50 or less,or 40 or less or 30 or less, or 20 or less. In other embodiments theShore A Hardness is 5 or more, 10 or more, or 15 or more. In certainapplications, such as packaging, the Shore A Hardness is preferably50-85. In another embodiment, the polymer has a Shore A hardness of20-90.

In another embodiment the POA has an Mz/Mn of 2 to 200, preferably 2 to150, preferably 10 to 100.

In another embodiment the POA has a Shear Adhesion Fail Temperature(SAFT—as measured by ASTM 4498) of 200° C. or less, or of 40 to 150° C.,or 60 to 130° C., or 65 to 110° C., or 70-80° C. In certain embodimentsSAFT's of 130-140° C. are preferred. In other embodiments, SAFT's of100-130° C. are preferred. In other embodiments, SAFT's of 110-140° C.are preferred.

In another embodiment the POA also has a Dot T-Peel on Kraft paper ofbetween 1 Newton and 10,000 Newtons, or 3 and 4000 Newtons, or between 5and 3000 Newtons, or between 10 and 2000 Newtons, or between 15 and 1000Newtons. Dot T-Peel is determined according to ASTM D 1876, as describedbelow.

In another embodiment the POA has a set time of several days to 1second, or 60 seconds or less, or 30 seconds or less, or 20 seconds orless, or 15 seconds or less, or 10 seconds or less, or 5 seconds orless, or 4 seconds or less, or 3 seconds or less, or 2 seconds or less,or 1 second or less.

In another embodiment the POA has an Mw/Mn of 2 to 75, or 4 to 60, or 5to 50, or 6 to 20.

In another embodiment the POA has an Mz of 1,000,000 or less, preferably15,000 to 1,000,000, or 20,000 to 800,000, or 25,000 to 350,000.

In another embodiment the POA has a strain at break (as measured by ASTMD-1708 at 25° C.) of 50 to 1000%, preferably 80 to 200%. In some otherembodiments the strain at break is 100 to 500%.

In another embodiment, the POA has a tensile strength at break (asmeasured by ASTM D-1708 at 25° C.) of 0.5 MPa or more, alternatively0.75 MPa or more, alternatively 1.0 MPa or more, alternatively 1.5 MPaor more, alternatively 2.0 MPa or more, alternatively 2.5 MPa or more,alternatively 3.0 MPa or more, alternatively 3.5 MPa or more.

In another embodiment the POA has a crystallization point (Tc) between20 and 110° C. In some embodiments the Tc is between 70 to 100° C. Inother embodiments the Tc is between 30 to 80° C. In other embodimentsthe Tc is between 20 to 50° C.

In some embodiment the POA has a slope of −0.1 or less, preferably −0.15or less, more preferably −0.25 or less in the trace of complex viscosityversus temperature as shown in FIG. 1 (as measured by ARES dynamicmechanical spectrometer operating at a frequency of 10 rad/s, with astrain of 20% under a nitrogen atmosphere, and a cooling rate of 10°C./min) over the range of temperatures from Tc+10° C. to Tc+40° C. Theslope is defined as a derivative of log (complex viscosity) with respectto temperature.

In another embodiment the POA has a Tc that is at least 10° C. below theTm, preferably at least 20° C. below the Tm, preferably at least 30° C.below the Tm, more preferably at least 35° C. below the Tm.

In another embodiment some olefin POA's have a melt index ratio (I₁₀/I₂)of 6.5 or less, preferably 6.0 or less, preferably 5.5 or less,preferably 5.0 or less, preferably 4.5 or less, preferably between 1 and6.0. (I₁₀ and I₂ are measured according to ASTM 1238 D, 2.16 kg, 190°C.).

In another embodiment some olefin POA's have a melt index (as determinedby ASTM 1238 D, 2.16 kg, 190 deg. C.) of 25 dg/min or more, preferably50 dg/min or more, preferably 100 dg/min or more, more preferably200dg/min or more, more preferably 500 dg/mn or more, more preferably2000 dg/min or more.

In another embodiment the POA has a range of crystallization of 10 to60° C. wide, preferably 20 to 50° C., preferably 30 to 45° C. in the DSCtraces. In DSC traces where there are two or more non-overlapping peaks,then each peak has a range of crystallization of 10 to 60° C. wide,preferably 20 to 50° C., preferably 30 to 45° C. in the DSC traces.

In another embodiment the POA has a molecular weight distribution(Mw/Mn) of at least 2, preferably at least 5, preferably at least 10,even more preferably at least 20.

In another embodiment the POA may have a unimodal, bimodal, ormultimodal molecular weight distribution (Mw/Mn) distribution of polymerspecies as determined by Size Exclusion Chromatography (SEC). By bimodalor multimodal is meant that the SEC trace has more than one peak orinflection points. An inflection point is that point where the secondderivative of the curve changes in sign (e.g., from negative to positiveor vice versus).

In another embodiment the POA has an Energy of activation of 8 to 15cal/mol. Energy of activation was calculated using the relationships ofcomplex viscosity and temperature over the region where thermal effectsare responsible for viscosity increase (assuming an Arrhenius-likerelationship).

In another embodiment the POA's have a cloud point of 200° C. or less,preferably 180° C. or less, preferably 160° C. or less, preferably 120°C. or less, preferably 100° C. or less. Likewise any composition thatthe POA is part of preferably has a cloud point of 200° C. or less,preferably 180° C. or less, preferably 160° C. or less, preferably 120°C. or less, preferably 100° C. or less.

In another embodiment the POA may also have one or more of thefollowing:

-   -   a) a peak melting point between 30 and 190° C., or between about        60 and 150° C., or between 80 and 130° C.; and/or    -   b) a viscosity of 8000 mPa·sec or less at 190° C. (as measured        by ASTM D 3236 at 190° C.); or 5000 or less, or 4000 or less, or        3000 or less, or 1500 or less, or between 250 and 6000 mPa·sec,        or between 500 and 5500 mPa·sec, or between 500 and 3000        mPa·sec, or between 500 and 1500 mPa·sec, or a viscosity of 8000        mPa·sec or less at 160° C. (as measured by ASTM D 3236 at 160°        C.); or 7000 or less, or 6000 or less, or 5000 or less, or 4000        or less, or 3000 or less, or 1500 or less, or between 250 and        6000 mPa·sec, or between 500 and 5500 mPa·sec, or between 500        and 3000 mPa·sec, or between 500 and 1500 mPa·sec; and/or    -   c) an H_(f) (Heat of fusion) of 70 J/g or less, or 60 J/g or        less, or 50 J/g or less; or 40 J/g or less, or 30 J/g or less,        or 20 J/g or less and greater than zero, or greater than 1 J/g,        or greater than 10 J/g, or between 10 and 50 J/g; and or    -   d) a Shore A Hardness (as measured by ASTM 2240) of 90 or less,        or 60 or less, or 50 or less, or 40 or less or 30 or less, or 20        or less; and or    -   e) a Shear Adhesion Fail Temperature (SAFT—as measured by        ASTM 4498) of 40 to 150° C., or 60 to 130° C., or 65 to 110° C.,        or 70-80° C.; and or;    -   f) a Dot T-Peel of between 1 Newton and 10,000 Newtons, or 3 and        4000 Newtons, or between 5 and 3000 Newtons, or between 10 and        2000 Newtons, or between 15 and 1000 Newtons; and/or    -   g) a set time of several days to 0.1 second, or 60 seconds or        less, or 30 seconds or less, or 20 seconds or less, or 15        seconds or less, or 10 seconds or less, or 5 seconds or less, or        4 seconds or less, or 3 seconds or less, or 2 seconds or less,        or 1 second or less; and/or    -   h) an Mw/Mn of greater than 1 to 75, or 2 to 60, or 2 to 50, or        3 to 20; and/or    -   i) an Mz of 500,000 or less, preferably 15,000 to 500,000, or        20,000 to 400,000, or 25,000 to 350,000.

Useful combinations of features include POA's having a Dot T-Peel ofbetween 1 Newton and 10,000 Newtons, or 3 and 4000 Newtons, or between 5and 3000 Newtons, or between 10 and 2000 Newtons, or between 15 and 1000Newtons and:

-   1) an Mw of 30,000 or less, a peak melting point between 60 and 190°    C., a Heat of fusion of 1 to 70 J/g, a branching index (g′) of 0.90    or less measured at the Mz of the polymer; and a melt viscosity of    8000 mPa·sec or less at 190° C.; or-   2) an Mz of 20,000 to 5,000,000 and a SAFT of 60 to 150° C.; or-   3) an Mz/Mn of 2-200 and a set time of 4 seconds or less; or-   4) an H_(f) (heat of fusion) of 20 to 50 J/g, an Mz or    20,000-500,000 and a shore hardness of 50 or less; or-   5) an Mw/Mn of greater than 1 to 50, a viscosity of 5000 or less    mPa·sec at 190° C.; or-   6) an Mw of 50,000 or less, a peak melting point between 60 and 190°    C., a heat of fusion of 2 to 70 J/g, a branching index (g′) of 0.70    or less measured at the Mz of the polymer, and a melt viscosity of    8000 mPa·sec or less at 190° C.

In a preferred embodiment, the POA comprises amorphous, crystalline andbranch-block molecular structures.

In a preferred embodiment the POA comprises at least 50 weight %propylene, preferably at least 60% propylene, alternatively at least 70%propylene, alternatively at least 80% propylene.

In another embodiment the POA has a glass transition temperature (Tg) asmeasured by ASTM E 1356 of 5° C. or less, preferably 0° C. or less,alternatively between 0° C. and −40° C., alternatively between −5° C.and −15° C.

In another embodiment the POA has an amorphous content of at least 50%,alternatively at least 60%, alternatively at least 70%, evenalternatively between 50 and 99%. Percent amorphous content isdetermined by subtracting the percent crystallinity from 100. Percentcrystallinity content is determined using Differential ScanningCalorimetry measurement according to ASTM E 794-85.

In another embodiment the POA has a crystallinity of 40% or less,alternatively 30% or less, alternatively 20% or less, even alternativelybetween 10% and 30%. Percent crystallinity content is determined usingDifferential Scanning Calorimetry measurement according to ASTM E794-85. In another embodiment, the polymers described herein have apercent crystallinity of between 5 and 40%, alternatively between 10 to30%.

In another embodiment the POA has a molecular weight distribution(Mw/Mn) of at least 1.5, preferably at least 2, preferably at least 5,preferably at least 10, even alternatively at least 20. In otherembodiments the Mw/Mn is 20 or less, 10 or less, even 5 or less.Molecular weight distribution generally depends on the catalysts usedand process conditions such as temperature, monomer concentration,catalyst ratio, if multiple catalysts are used, and the presence orabsence of hydrogen. Hydrogen may be used at amounts up to 2 weight %,but is preferably used at levels of 50 to 500 ppm.

In another embodiment the POA is found to have at least two molecularweights fractions are present at greater than 2 weight %, preferablygreater than 20 weight %, each based upon the weight of the polymer asmeasured by Gel Permeation Chromatography. The fractions can beidentified on the GPC trace by observing two distinct populations ofmolecular weights. An example would be a GPC trace showing a peak at20,000 Mw and another peak at 50,000 Mw where the area under the firstpeak represents more than 2 weight % of the polymer and the area underthe second peak represents more than 2 weight % of the polymer.

In another embodiment the POA has 20 weight % or more (based upon theweight of the starting polymer) of hexane room temperature solublefraction, and 70 weight % or less, preferably 50 weight % or less ofSoxhlet boiling heptane insoluble, based upon the weight of the polymer.Soxhlet heptane insoluble refers to one of the fractions obtained when asample is fractionated using successive solvent extraction technique.The fractionations are carried out in two steps: one involves roomtemperature solvent extraction, the other soxhlet extraction. In theroom temperature solvent extraction, about one gram of polymer isdissolved in 50 ml of solvent (e.g., hexane) to isolate the amorphous orvery low molecular weight polymer species. The mixture is stirred atroom temperature for about 12 hours. The soluble fraction is separatedfrom the insoluble material using filtration under vacuum. The insolublematerial is then subjected to a Soxhlet extraction procedure. Thisinvolves the separation of polymer fractions based on their solubilityin various solvents having boiling points from just above roomtemperature to 110° C. The insoluble material from the room temperaturesolvent extraction is first extracted overnight with a solvent such ashexane and heptane (Soxhlet); the extracted material is recovered byevaporating the solvent and weighing the residue. The insoluble sampleis then extracted with a solvent having higher boiling temperature suchas heptane and after solvent evaporation, it is weighed. The insolubleand the thimble from the final stage are air-dried in a hood toevaporate most of the solvent, then dried in a nitrogen-purged vacuumoven. The amount of insoluble left in the thimble is then calculated,provided the tare weight of the thimble is known.

In another embodiment, the POA's have a heptane insoluble fraction 70weight % or less, based upon the weight of the starting polymer, and theheptane insoluble fraction has branching index g′ of 0.9 (preferably0.7) or less as measured at the Mz of the polymer. In a preferredembodiment the POA's also have at least 20 weight % hexane solublefraction, based upon the weight of the starting polymer. In anotherembodiment, the POA's have a heptane insoluble fraction 70 weight % orless, based upon the weight of the starting polymer and a Mz between20,000 and 5000,000 of the heptane insoluble portion. In a preferredembodiment the POA's also have at least 20 weight % hexane solublefraction, based upon the weight of the starting polymer. In anotherembodiment the POA's have a hexane soluble portion of at least 20 weight%, based upon the weight of the starting polymer.

In another embodiment the POA comprises propylene and 15 mole % ethyleneor less, preferably 10 mole % ethylene or less, more preferably 9 mole %ethylene or less, more preferably 8 mole % ethylene or less, morepreferably 7 mole % ethylene or less, more preferably 6 mole % ethyleneor less, more preferably 5 mole % ethylene or less, more preferably 4mole % ethylene or less, more preferably 3 mole % ethylene or less, morepreferably 2 mole % ethylene or less, more preferably 1 mole % ethyleneor less.

In another embodiment the POA comprises less than 5 mole % of ethylene,preferably less than 4.5 mole % ethylene, preferably less than 4.0 mole% ethylene, alternatively less than 3.5 mole % ethylene, alternativelyless than 3.0 mole % ethylene, alternatively less than 2.5 mole %ethylene, alternatively less than 2.0 mole % ethylene, alternativelyless than 1.5 mole % ethylene, alternatively less than 1.0 mole %ethylene, alternatively less than 0.5 mole % ethylene, alternativelyless than 0.25 mole % ethylene, alternatively 0 mole % ethylene.

For ease of reference the polymer produced by the second catalyst havingat least 20% crystallinity may also be referred to as the“semi-crystalline polymer” and the polymer produced by the firstcatalyst component having a crystallinity of less than 5% may bereferred to as the “amorphous polymer.”

In another embodiment of this invention the POA's have a characteristicthree-zone complex viscosity-temperature pattern, as shown in FIG. 1.The temperature dependence of complex viscosity was measured using ARESdynamic mechanical spectrometer operating at a frequency of 10 rad/s,with a strain of 20% under a nitrogen atmosphere, and a cooling rate of10° C./min. The sample was first molten then gradually cooled down toroom temperature while monitoring the build-up in complex viscosity.Above the melting point, which is typical of polymer processingtemperature, the complex viscosity is relatively low (Zone I) andincreases gradually with decreasing temperature. In zone II, a sharpincrease in complex viscosity appears as temperature is dropped. Thethird zone (Zone III) is the high complex viscosity zone, which appearsat lower temperatures corresponding to application (end use)temperatures. In Zone III the complex viscosity is high and variesslightly with further decrease in temperature. Such a complex viscosityprofile provides, in hot melt adhesive applications, a desirablecombination of long opening time at processing temperatures and fast settime at lower temperatures.

In a preferred embodiment, the POA's have less than 1 mol % ethylene,have at least 2 mol % (CH₂)₂ units, preferably 4 mol %, preferably 6 mol%, more preferably 8 mol %, more preferably 10 mol %, more preferably 12mol %, more preferably 15 mol %, more preferably 18 mol %, morepreferably 5 mol % as measured by Carbon 13 NMR as described below.

In an another embodiment, the POA's have between 1 and 10 mol %ethylene, have at least 2+X mol % (CH₂)₂ units, preferably 4+X mol %,preferably 6+X mol %, more preferably 8+X mol %, more preferably 10+Xmol %, more preferably 12+X mol %, more preferably 15+X mol %, morepreferably 18+X mol %, more preferably 20+X mol %, where X is the mole %of ethylene, and the (CH₂)₂ units are determined by Carbon 13 NMR asdescribed below.

In a preferred embodiment, the POA's have less than 1 mol % ethylene,have an amorphous component (which is defined to be that portion of thepolymer composition that has a crystallinity of less than 5%) whichcontains at least 3 mol % (CH₂)₂ units, preferably 4 mol %, preferably 6mol %, more preferably 8 mol %, more preferably 10 mol %, morepreferably 12 mol %, more preferably 15 mol %, more preferably 18 mol %,more preferably 20 mol % as measured by Carbon 13 NMR as describedbelow.

In an another embodiment, the POA's have between 1 and 10 mol % ethyleneand have an amorphous component (which is defined to be that portion ofthe polymer composition that has a crystallinity of less than 20%) whichcontains at least 3+X mol % (CH₂)₂ units, preferably 4+X mol %,preferably 6+X mol %, more preferably 8+X mol %, more preferably 10+Xmol %, more preferably 12+X mol %, more preferably 15+X mol %, morepreferably 18+X mol %, more preferably 20+X mol %, where X is the mole %of ethylene, and the (CH₂)₂ units are determined by Carbon 13 NMR asdescribed below.

In a preferred embodiment the POA's comprise an olefin homopolymer orcopolymer, having less than 5 mol % ethylene, and comprising one or moreC3 to C40 alpha olefins. In another preferred embodiment the POA, havingless than 5 mol % ethylene, further comprises one or more diolefincomonomers, preferably one or more C4 to C40 diolefins.

In a preferred embodiment the POA is a propylene homopolymer orcopolymer. The comonomer is preferably a C4 to C20 linear, branched orcyclic monomer, and in one embodiment is a C4 to C12 linear or branchedalpha-olefin, preferably butene, pentene, hexene, heptene, octene,nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1, and the like. Ethylene may bepresent at 5 mol % or less.

In another embodiment the POA is a copolymer of one or more linear orbranched C3 to C30 prochiral alpha-olefins or C5 to C30 ring containingolefins or combinations thereof capable of being polymerized by eitherstereospecific and non-stereospecific catalysts. Prochiral, as usedherein, refers to monomers that favor the formation of isotactic orsyndiotactic polymer when polymerized using stereospecific catalyst(s).

In a preferred embodiment, the POA may be a polymer of two or morelinear, branched, cyclic-containing, or a mixture of these structures.Preferred linear alpha-olefins include C3 to C8 alpha-olefins, morepreferably propylene, 1-butene, 1-hexene, and 1-octene, even morepreferably propylene or 1-butene. Preferred branched alpha-olefinsinclude 4-methyl-1-pentene, 3-methyl-1-pentene, and3,5,5-trimethyl-1-hexene, 5-ethyl-1-nonene. Preferredaromatic-group-containing monomers contain up to 30 carbon atoms.Suitable aromatic-group-containing monomers comprise at least onearomatic structure, preferably from one to three, more preferably aphenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C1 to C10 alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C1 to C10 alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene,cyclohexene, cyclobutene, vinyladamantane and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C4 to C30, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In a preferred embodiment one or more dienes are present in the POA atup to 10 weight %, preferably at 0.00001 to 1.0 weight %, preferably0.002 to 0.5 weight %, even more preferably 0.003 to 0.2 weight %, basedupon the total weight of the composition. In some embodiments 500 ppm orless of diene is added to the polymerization, preferably 400 ppm orless, preferably or 300 ppm or less. In other embodiments at least 50ppm of diene is added to the polymerization, or 100 ppm or more, or 150ppm or more.

In a preferred embodiment the polymer is homo-polypropylene. In anotherpreferred embodiment the POA comprises propylene, less than 5 mol %ethylene, and at least one divinyl comonomer. In another preferredembodiment the POA comprises propylene and at least one divinylcomonomer.

The POA's described herein may be produced by a process comprising:

-   -   1) selecting a first catalyst component capable of producing a        polymer having a Mw of 100,000 or less and a heat of fusion of        10 J/g or less under the selected reaction conditions;    -   2) selecting a second catalyst component capable of producing        polymer having an Mw of 100,000 or less and a crystallinity of        20% or more under the selected reaction conditions; and    -   3) contacting the catalyst components in the presence of one or        more activators with one or more olefins, in a reaction zone.

The POA's described herein may be produced by a process comprising:

-   -   1) selecting a first catalyst component capable of producing a        polymer having an Mw of 100,000 or less and a heat of fusion of        10 J/g or less;    -   2) selecting a second catalyst component capable of producing        polymer having an Mw of 100,000 or less and a crystallinity of        20% or more;    -   3) contacting the catalyst components in the presence of one or        more activators with one or more olefins and one or more dienes,        in a reaction zone.

The POA's described herein may be produced by a process comprising:

-   -   1) selecting a first catalyst component capable of producing a        polymer having an Mw of 100,000 or less and a heat of fusion of        10 J/g or less, capable of polymerizing macromonomers having        reactive termini;    -   2) selecting a second catalyst component capable of producing        macromonomers having reactive termini, an Mw of 100,000 or less        and a crystallinity of 20% or more; and    -   3) contacting the catalyst components in the presence of one or        more activators with one or more olefins, and optionally a        diolefin in a reaction zone.

The POA's described herein may be produced by a process comprising:

-   -   1) selecting a first catalyst component capable of producing a        polymer having an Mw of 50,000 or less and a heat of fusion of        10 J/g or less, capable of polymerizing macromonomers having        reactive termini;    -   2) selecting a second catalyst component capable of producing        macromonomers having reactive termini, an Mw of 30,000 or less        and a crystallinity of 20% or more;    -   3) contacting the catalyst components in the presence of one or        more activators with propylene, and optionally other olefins, in        a reaction zone.

The POA's may be produced by a continuous process comprising:

-   -   1) selecting a first catalyst component capable of producing a        polymer having an Mw of 100,000 or less, preferably 80,000 or        less, preferably 60,000 or less and a crystallinity of 5% or        less, preferably 3% or less, more preferably 2% or less, under        selected polymerization conditions;    -   2) selecting a second catalyst component capable of producing        polymer having an Mw of 100,000 or less, preferably 80,000 or        less, preferably 60,000 or less and a crystallinity of 30% or        more, preferably 50% or more, more preferably 60% or more at the        selected polymerization conditions;    -   3) contacting, under the selected polymerization conditions, the        catalyst components in the presence of one or more activators        with one or more C3 to C40 olefins, preferably one or more C3 to        C12 olefins, preferably C3 and one or more C4 to C20 comonomers,        and, optionally one or more diolefins, preferably a C4 to C20        diene;    -   4) at a temperature of greater than 100° C., preferably greater        than 105° C., more preferably greater than 110° C., more        preferably greater than 115° C.;    -   5) at a residence time of 120 minutes or less, preferably 50        minutes or less, preferably 40 minutes, preferably 30 minutes or        less, preferably 25 minutes or less, more preferably 20 minutes        or less, more preferably 15 minutes or less, more preferably at        10 minutes or less, more preferably at 5 minutes or less, or        alternately between 120 minutes and 60 minutes;    -   6) wherein the ratio of the first catalyst to the second        catalyst is from 1:1 to 50:1, preferably 1:1 to 40:1, more        preferably 1:1 to 1:30;    -   7) wherein the activity of the catalyst components is at least 3        kilograms, preferably at least 50 kilograms, more preferably at        least 100 kilograms, more preferably at least 200 kilograms,        more preferably, 300 kilograms, more preferably 400 kilograms,        more preferably 500 kilograms of polymer per gram of the        catalyst mixture; and wherein at least 80%, preferably at least        85%, more preferably at least 90%, more preferably at least 95%        of the olefins are converted to polymer.

In another embodiment at least 20% or more of the olefins are convertedto polymer, preferably 20% or more, more preferably 60% or more, morepreferably 75% or more, more preferably 85% or more, more preferably 95%or more.

In a preferred embodiment the process described above takes place in asolution phase, slurry or bulk phase polymerization process.

By continuous is meant a system that operates (or is intended tooperate) without interruption or cessation. For example, a continuousprocess to produce a polymer would be one where the reactants arecontinually introduced into one or more reactors and polymer product iscontinually withdrawn.

In another preferred embodiment, in the process described above theconcentrations of the reactants vary by 20% or less in the reaction zoneduring the residence time, preferably by 15% or less, more preferably by10% or less. In a preferred embodiment the concentration of themonomer(s) remains constant in the reaction zone during the residencetime. Preferably the concentration of the monomer(s) varies by 20% orless, preferably by 15% or less, more preferably by 10% or less, morepreferably by 5% or less.

In a preferred embodiment the concentration of the catalyst componentsremains constant in the reaction zone during the residence time.Preferably the concentration of the monomer(s) varies by 20% or less,preferably by 15% or less, more preferably by 10% or less, morepreferably by 5% or less.

In a preferred embodiment the concentration of the activator(s) remainsconstant in the reaction zone during the residence time. Preferably theconcentration of the monomer(s) varies by 20% or less, preferably by 15%or less, more preferably by 10% or less, more preferably by 5% or less.

In another preferred embodiment a third catalyst (or more) may bepresent in the processes described above. The third catalyst may be anyof the catalyst components listed herein. Preferred third catalystsinclude catalysts that are capable of producing waxes. Other preferredthird catalysts may include any catalyst described herein. One mayselect two or more catalysts to produce various macromonomers havingreactive termini, used in combination with a catalyst that canpolymerize such macromonomers. One may select two or more catalysts thatcan polymerize macromonomers and one catalyst that can producemacromonomers with reactive termini. Likewise one could also selectthree catalysts that produce different polymers under the same reactionconditions. For example one could select a catalyst that produces asomewhat crystalline polymer, one that produces a very crystallinepolymer and one that produces an amorphous polymer, any of which mayproduce macromonomers with reactive termini or polymerize polymershaving reactive termini. Similarly one could select two catalysts, onethat produces crystalline polymers and one that produces an amorphouspolymer, any of which may make macromonomers with reactive termini orpolymerize polymers having reactive termini. Likewise one could select acatalyst that produces a somewhat crystalline polymer, one that producesa wax and one that produces an amorphous polymer, any of which may makemacromonomers with reactive termini or polymerize polymers havingreactive termini.

By reaction zone is meant an area where the activated catalyst andmonomers can react.

By macromonomers having reactive termini is meant a polymer havingtwelve or more carbon atoms (preferably 20 or more, more preferably 30or more, more preferably between 12 and 8000 carbon atoms) and having avinyl, vinylidene, vinylene or other terminal group that can bepolymerized into a growing polymer chain. By capable of polymerizingmacromonomer having reactive termini is meant a catalyst component thatcan incorporate a macromonomer (which tend to be molecules larger than atypical single monomer such as ethylene or propylene), having reactivetermini into a growing polymer chain. Vinyl terminated chains aregenerally more reactive than vinylene or vinylidene terminated chains.

In a particular embodiment the POA is produced by copolymerizing one ormore C₃ or higher alpha-olefins and/or one or more di-vinyl monomers,and optionally up to 5 mol % ethylene, in the presence of at least onestereospecific catalyst system and at least one other catalyst system inthe same polymerization medium. Preferably, the polymerizations arecarried out simultaneously in the presence of both catalysts. Thepolymer so produced may contain amorphous polymer segments andcrystalline polymer segments in which at least some of the segments arelinked. Typically the amorphous and the crystalline polymer segments arecopolymers of one or more alpha-olefins (optionally including up to 5mol % ethylene) and/or one or more monomers having at least twoolefinically unsaturated bonds. Both of these unsaturated bonds aresuitable for and readily incorporated into a growing polymer chain bycoordination polymerization using either the first or second catalystsystems independently such that the di-olefin is incorporated intopolymer segments produced by both catalysts in the mixed catalyst systemaccording to this invention. In a preferred embodiment these monomershaving at least two olefinically unsaturated bonds are di-olefins,preferably di-vinyl monomers. Crosslinking of at least a portion of themixture of polymer segments is believed to be accomplished during thepolymerization of the composition by incorporation of a portion ofdi-vinyl comonomers into two polymer segments, thus producing acrosslink between those segments.

In another embodiment, POAs containing amorphous and semi-crystallinecomponents may be prepared in a single reactor to yield desired propertybalance. In particular, aPP-g-scPP branch structures may be producedin-situ in a continuous solution reactor using mixed catalysts andpropylene as the preferred feed. In one embodiment stereospecificbridged bis-indenyl group 4 catalysts can be selected to producesemicrystalline PP macromonomers. (All references to the Periodic Tableof the Elements are to the new notation of the Table published inChemical and Engineering News, 63(5), 27, 1985.) A bridgedmono-cyclopentadienyl heteroatom group 4 catalyst can be used to buildamorphous PP (aPP) backbone while simultaneously incorporating some ofthe semi-crystalline macromonomers (scPP). This is believed to producean aPP-g-scPP structure where the “-g-” indicates that the polymer typesare at least partially grafted. By selecting the catalysts, thepolymerization reaction conditions, and/or by introducing a dienemodifier, the amorphous and crystalline components can be linkedtogether to produce various branch-block structures. To effectivelyincorporate into a growing chain, a macromonomer with vinyl end group ispreferred. Other types of chain end unsaturations (vinylene andvinylidene) can also be used. While not wishing to be bound by theory,branch-block copolymer is believed to comprise an amorphous backbonehaving crystalline side chains originating from the scPP macromonomersand the sidechains are believed to be polypropylene macromonomers, whichcan be prepared under solution polymerization conditions with catalystssuitable for preparing either of isotactic or syndiotacticpolypropylene.

Any catalyst compound that can produce the desired polymer species (i.e.a polymer having an Mw of 100,000 or less and a heat of fusion of 70 J/gor less, or a polymer having an Mw of 100,000 or less and acrystallinity of 40% or less) may be used in the practice of thisinvention.

Functionalized Component

Typically, the component to be functionalized is combined with a freeradical initiator and a grafting monomer or other functional group (suchas maleic acid or maleic anhydride) and is heated to react the monomerwith the polymer, copolymer, oligomer, etc to form the functionalizedcomponent. Multiple methods exist in the art for functionalizingpolymers that may be used with the polymers described here. Theseinclude, not are not limited to, selective oxidation, free radicalgrafting, ozonolysis, epoxidation, and the like.

Preferred functional components have an Mw of 1000 to 20,000, preferably2000 to 15,000, more preferably 3000 to 10,000.

Examples of suitable functionalized components for use in this inventioninclude, but are not limited to, functionalized olefin polymers, (suchas functionalized C2-C40 homopolymers, functionalized C2-C40 copolymers,functionalized higher Mw waxes), functionalized oligomers, (such asfunctionalized low Mw waxes, functionalized tackifiers), beta nucleatingagents and combinations thereof.

Useful functionalized olefin polymers and copolymers useful in thisinvention include maleated polyethylene, maleated metallocenepolyethylene (such as EXACT and EXCEED-available from ExxonMobilChemical Company in Houston, Tex.—which have been functionalized asdescribed herein), maleated metallocene polypropylene (such asACHIEVE—available from ExxonMobil Chemical Company in Houston,Tex.—which has been functionalized as described herein), maleatedethylene propylene rubber, maleated polypropylene, maleated ethylenecopolymers (such as EXXELOR™ by ExxonMobil Chemical Company in Houston,Tex., particularly EXXELOR VA 1801, 1803, 1840 and EXXELOR PO 1015 and1020), functionalized polyisobutylene (typically functionalized withmaleic anhydride typically to form a succinic anhydride), and the like.

Preferred functionalized waxes useful as functionalized componentsherein include those modified with an alcohol, an acid, a ketone, ananhydride and the like. Preferred examples include waxes modified bymethyl ketone, maleic anhydride or maleic acid. Preferred functionalizedwaxes useful herein include maleated polypropylene was available fromChusei under the tradename MAPP 40, maleated metallocene waxes (such asTP LICOCENE PP1602 available from Clariant, in Augsburg, Germany);maleated polyethylene waxes and maleted polypropylene waxes availablefrom Eastman Chemical in Kingsport Tenn. under the trade names EPOLENEC-16, EPOLENE C-18, EPOLENE E43, EPOLENE G-3003; maleated polypropylenewax LICOMONT AR 504 available from Clariant; grafted functional polymersavailable from Dow Chemical Co., under the tradenames AMPLIFY EA 100,AMPLIFY EA 102, AMPLIFY 103, AMPLIFY GR 202, AMPLIFY GR 205, AMPLIFYGR207, AMPLIFY GR 208, AMPLIFY GR 209, AMPLIFY VA 200; CERAMER maleatedethylene polymers available from Baker Hughes under the tradenameCERAMER 1608, CERAMER 1251, CERAMER 67, CERAMER 24; and ethylene methylacrylate co and terpolymers.

Useful waxes include polypropylene waxes having an Mw weight of 15,000for less, preferably from 3000 to 10,000 and a crystallinity of 5% ormore, preferably 10% or more having a functional group content(preferably maleic anhydride) of up to 10 weight %.

Additional preferred functionalized polymers for use as functionalcomponents herein include A-C X596A, A-C X596P, A-C X597A, A-C X597P,A-C X950P, A-C X1221, A-C 395A, A-C 395A, A-C 1302P, A-C 540, A-C 54A,A-C 629, A-C 629A, and A-C 307, A-C 307A available from Honeywell.

Preferred functionalized polymers have crystallinity of at least 5%,preferably at least 10%.

UNILIN long chain alcohols, available from Baker Hughes are also usefulas functionalized components herein, particularly UNILIN 350, UNILIN425, UNILIN 550, and UNILIN 700.

UNICID linear, primary carboxylic acids, available from Baker Hughes arealso useful as functionalized components herein, particularly UNICID350, UNICID 425, UNICID 550, and UNICID 700.

Preferred functionalized hydrocarbon resins that may be used asfunctionallized components in this invention include those described inWO 03/025084, WO 03/025037, WO 03/025036, and EP 1 295 926 A1 which areincorporated by reference herein.

In a preferred embodiment a hydrocarbon resin is functionalized with anunsaturated acids or anhydrides containing at least one double bond andat least one carbonyl group and used as the functionalized component ofthis invention. Preferred hydrocarbon resins that can be functionalizedare listed below as tackifiers. Representative acids include carboxylicacids, anhydrides, esters and their salts, both metallic andnon-metallic. Preferably the organic compound contains an ethylenicunsaturation conjugated with a carbonyl group (—C═O). Examples includemaleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha.methylcrotonic, and cinnamic acids as well as their anhydrides, esters andsalt derivatives. Particularly preferred functional groups includemaleic acid and maleic anhydride. Maleic anhydride is particularlypreferred. The unsaturated acid or anhydride is preferably present atabout 0.1 weight % to about 10 weight %, preferably at about 0.5 weight% to about 7 weight %, even more preferably at about 1 to about 4 weight%, based upon the weight of the hydrocarbon resin and the unsaturatedacid or anhydride. In a preferred embodiment the unsaturated acid oranhydried comprises a carboxylic acid or a derivative thereof selectedfrom the group consisting of unsaturated carboxylic acids, unsaturatedcarboxylic acid derivatives selected from esters, imides, amides,anhydrides and cyclic acid anhydrides or mixtures thereof.

In some embodiments, however the functionalized component does notcomprise functionalized hydrocarbon resins. In some embodiments,functionalized hydrocarbon resin is present at 5 weight % or less,preferably 4 weight % or less, preferably 3 weight % or less, preferablyat 2 weight % or less, preferably at 1 weight % or less, preferably at0.5 weight % or less, preferably at 0.1 weight % or less, preferably at0.01 weight % or less, preferably at 0.001 weight % or less, based uponthe weight of the adhesive. In some preferred embodiments,functionalized hydrocarbon resin is not present in the adhesive.

Preferred beta nucleating agents useful in this invention include: amidecompound selected from the group consisting of:

-   (1) an amide compound of the formula    R²—NHCO—R¹—CONH—R³  (1)    wherein R¹ is a residue formed by elimination of the two carboxyl    groups of a C3-26 saturated or unsaturated aliphatic dicarboxylic    acid, a C6-30 saturated or unsaturated alicyclic dicarboxylic acid    or a C8-30 aromatic dicarboxylic acid; R² and R³ are the same or    different and each represents a C3-18 cycloalkyl group, a C3-12    cycloalkenyl group, or a substituted or unsubstituted phenyl or    cyclohexyl group;-   (2) an amide compound of the formula    R⁹—CONH—R⁸—NHCO—R¹⁰  (2)    wherein R⁸ is a residue formed by elimination of the two amino    groups of a C1-24 saturated or unsaturated aliphatic diamine, a    C4-28 alicyclic diamine, a C4-14 heterocyclic diamine or a C6-28    aromatic diamine; R⁹ and R¹⁰ are the same or different and each    represents a C3-12 cycloalkyl group, a C3-12 cycloalkenyl group, or    a substituted or unsubstituted phenyl or cyclohexyl group; and-   (3) an amide compound of the formula    R¹⁶—CONH—R¹⁵—CONH—R¹⁷  (3)    wherein R¹⁵ is a residue formed by elimination of one amino group    and one carboxyl group from of a C2-29 saturated or unsaturated    aliphatic amino acid, C7-13 saturated or unsaturated alicyclic amino    acid or C7-15 aromatic amino acid; R¹⁶ and R¹⁷ are the same or    different and R¹⁶ has the same meaning as R⁹ or R¹⁰ in the    formula (2) and R¹⁷ has the same meaning as R² or R³ in the formula    (1).

Preferred beta nucleating agents useful in this invention include:N,N′-diphenylhexanediamide, N,N′-dicyclohexylterephthalamide,N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide,N,N′-dicyclohexanecabonyl-p-phenylenediamine,N,N′-dibenzoyl-1,5-diaminonaphthalene,N,N′-dibenzoyl-1,4-diaminocyclohexane orN,N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane,N-cyclohexyl-4-(N-cyclohexylcarbonylamino)benzamide,N-phenyl-5-(N-benzoylamino)pentanamide, sorbitol, salicyclic acid,p-hydroxybenzoic acid, zinc 3,5-di-tert-butylsalicyclate, 2-naphthoicacid, phenyl acetic acid, terephthalic acid, anthranilic acid,3,3-diphenylpropionic, tetra butyl ammonium chloride, naphthalic acid,benzoin, ascorbic acid, adipic acid, tertabutyl benzoate,dodecylbenzenesulfonic acid sodium salt, 4-dodecylbenzenesulfonic acid,4,4-bis(4-hydroxyphenyl)valeric acid, diphenic acid, 4-isopropylbenzoicacid, Millad 3988tm, neodecanoic acid, abietic acid, sodium benzoate,succinic anhydride, phenol, benzoic acid, benzyl alcohol, benzyl amine,alkyl substituted succinates (preferably C1 to C40 alkyl substitutedsuccinates), substituted di(benzylidene)-D-sorbitols,1,3:2,4-di(benzylidene)-D-sorbitol,1,3:2,4-bis(3,4-dimethylbenzylidene)-D-sorbitol, red quinacridone dye,

Preferred beta nucleating agents useful in this invention include theagents listed in U.S. Pat. No. 5,231,126; the single walled carbonnanotubes described in J. Phys. Chem. B. 2002, 106, 5852-5858; ModernPlastics, September 1998, page 82.

Preferred beta nucleating agents useful in this invention includebeta-spherulite nucleating agents. U.S. Pat. No. 4,975,469 and thereferences cited therein, incorporated herein by reference, disclosebeta-spherulite nucleating agents such as the gamma-crystalline form ofa quinacridone colorant, the bisodium salt of orthophthalic acid, thealuminum salt of 6-quinizarin sulfonic acid and to a lesser degreeisophthalic and terephthalic acids. The nucleating agents are typicallyused in the form of powdered solids. To produce beta-spherulitesefficiently the powder particles of the nucleating agent should be lessthan 5 microns in diameter and preferably no greater than 1 micron indiameter. The preferred beta-spherulite nucleating agent that may beused in the polymeric compositions of this invention is thegamma-crystalline form of a quinacridone colorant. One form of thequinacridone colorant is red quinacridone dye, hereinafter also referredto as “Q-dye”, having the structure shown in U.S. Pat. No. 4,975,469.

In a preferred embodiment the beta nucleating agent is present in theadhesive at up to 5 weight %, preferably 0.0001 to 3 weight %,preferably 0.1 to 2 weight %, preferably at 0.01 to 10 ppm, based uponthe weight of the blend.

For more information on beta nucleation and beta nucleating agents,please see pages 137-138 (and the references cited therein) of PropyleneHandbook, Edward P. Moore, ed. Hanser publishers, New York, 1996.

The polymers, copolymers, oligomers, etc and blends thereof, may befunctionalized for use in the present invention such that functionalgroups may be grafted onto the polymers, preferably utilizing radicalcopolymerization of an functional group, also referred to herein asgraft copolymerization. The end result being a functionalized polymer,copolymer oligomer, hydrocarbon resin, etc, abbreviated herein asAA-g-XX, wherein AA represents the specific type of polymer, copolymer,oligomer or hydrocarbon resin being functionalized, XX refers to thefunctional group or compounds with which the polymer was functionalizedwith, and -g- represents grafting between the two moieties.

Preferred functional groups include any compound with a weight averagemolecular weight of 1000 or less, preferably 750 or less, that containone or more a heteroatoms and or one or more unsaturations. Preferablythe functional group is a compound containing a heteroatom, such asmaleic anhydride. Preferred functional groups include organic acids,organic amides, organic amines, organic esters, organic anhydrides,organic alcohols, organic acid halides (such as acid chlorides, acidbromides, etc.) organic peroxides, and salts thereof.

Examples of preferred functional groups useful in this invention includecompounds comprising a carbonyl bond such as carboxylic acids, esters ofthe unsaturated carboxylic acids, acid anhydrides, di-esters, salts,amides, imides, aromatic vinyl compounds hydrolyzable unsaturated silanecompounds and unsaturated halogenated hydrocarbons.

Examples of particularly preferred functional groups useful in thisinvention include, but are not limited, to maleic anhydride, citraconicanhydride, 2-methyl maleic anhydride, 2-chloromaleic anhydride,2,3-dimethylmaleic anhydride, bicyclo[2,2,1]-5-heptene-2,3-dicarboxylicanhydride and 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylicacid, methacrylic acid, maleic acid, fumaric acid, itaconic acid,citraconic acid, mesaconic acid, crotonic acid,bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,&g,lo-octahydronaphthalene-2,3-dicarboxylic acid anhydride,2-oxa-1,3-diketospiro(4.4)non-7-ene,bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaricacid, tetrahydrophtalic anhydride, norborn-5-ene-2,3-dicarboxylic acidanhydride, nadic anhydride, methyl nadic anhydride, himic anhydride,methyl himic anhydride, andx-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride(XMNA).

Examples of esters of unsaturated carboxylic acids useful in thisinvention as functional groups include methyl acrylate, ethyl acrylate,butyl acrylate, methyl methacrylate, ethyl methacrylate and butylmethacrylate.

Examples of hydrolyzable unsaturated silane compounds useful asfunctional groups in this invention include radical polymerizableunsaturated group and an alkoxysilyl group or a silyl group in itsmolecule, such that the compound has a hydrolyzable silyl group bondedto a vinyl group and/or a hydrolyzable silyl group bonded to the vinylgroup via an alkylene group, and/or a compound having a hydrolyzablesilyl group bonded to an ester or an amide of acrylic acid, methacrylicacid or the like. Examples thereof include vinyltrichlorosilane,vinyltris(beta-methoxyethoxy)silane, vinyltriethoxysilane,vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilanemonovinylsilane and monoallylsilane.

Examples of unsaturated halogenated hydrocarbons useful as functionalgroups in this invention include vinyl chloride and vinylidene chloride.

In a preferred embodiment, the functionalized components includepropylene, and may be grafted with maleic anhydride (MA), to producepolypropylene copolymer grafted maleic anhydride, wherein the maleicanhydride is covalently bonded to the polymer chain of the polymericcomposition. The anhydride functionality grafted onto the polypropylenecopolymer may remain as an anhydride, may be oxidized into acidfunctional groups, and/or may be further reacted by processes known inthe art to induce other functional groups such as amides, amines, andthe like.

Preferable examples of the radical initiator used in the graftcopolymerization include organic peroxides such as benzoyl peroxide,methyl ethyl ketone peroxide, cyclohexanone peroxide,t-butylperoxyisopropyl carbonate, di-ti-butyl perphthalate,2,5-dimethyl-2,5-di(t-butylperoxy)hexene,2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3, di-t-butyl peroxide, cumenehydroperoxide, t-butyl hydroperoxide, dilauryl peroxide and dicumylperoxide.

The functionalized polymer of the present invention may thus be obtainedby heating the polymer and the radical polymerizable functional group inthe presence of the radical initiator at, near, or above a decompositiontemperature of the radical initiator.

In some embodiments, no particular restriction need be put on the amountof the functional group to be used, accordingly, conventional conditionsfor functionalizing, for example, an isotactic polypropylene, can beutilized as is in the practice of this invention. Since in some casesthe efficiency of the copolymerization is relatively high, the amount ofthe functional group may be small. In an embodiment, the amount of thefunctional group to be incorporated into the polymer, copolymer oroligomer is preferably from about 0.001 to 50 wt % functional group withrespect to the total weight of the polymer. In an preferred embodiment,the amount of the maleic anhydride to be incorporated into the polymer,copolymer or oligomer is preferably from about 0.001 to 50 wt % MA withrespect to the total weight of the polymer.

The radical initiator is preferably used in a ratio of from 0.00001 to10 wt %, based on the weight of the functional group. The heatingtemperature depends upon whether or not the reaction is carried out inthe presence of a solvent, but it is usually from about 50° C. to 350°C. When the heating temperature is less than 50° C., the reaction may beslow and thus efficiency may be low. When it is more than 350° C.,decomposition of the PP copolymer may occur. The functionalizedcomponent may be functionalized with an functional group utilizing asolvent based functionalization process and/or utilizing a melt basedfunctionalization process without a solvent.

In the solvent based process, the reaction may be carried out using thepolymer in the form of a solution or a slurry having a concentration offrom 0.1 to 50 wt % in the presence of a halogenated hydrocarboncompound having 2 to 20 carbon atoms, an aromatic compound, ahalogenated aromatic compound, an alkyl substituted aromatichydrocarbon, a cyclic hydrocarbon, and/or a hydrocarbon compound having6 to 20 carbon atoms which is stable to the radicals.

In the functionalization process utilizing a melt basedfunctionalization process without a solvent, the reaction may be carriedout in the absence of the solvent in a device such as an extruder whichcan sufficiently produce physical contact between what may be a highlyviscous polymer. In the latter case, the reaction is usually effected ata relatively high temperature, as compared with the reaction in thestate of the solution.

Other methods for functionalizing polymers that may be used with thepolymers described herein include, but are not limited to, selectiveoxidation, ozonolysis, epoxidation, and the like, both in solution orslurry (i.e., with a solvent), or in a melt (i.e., without a solvent).

The functionalized components may be a single polymer which has beenfunctionalized as described herein. In another embodiment, thefunctionalized component of the present invention may be a blend ofpolymers which are functionalized together during a single process. Thefunctionalized components of the present invention may also include aplurality of functionalized components which are combined after beingindividually functionalized, or any combination thereof.

In the present invention, the graft polymerization (grafting of thepolymer) can be carried out in an aqueous medium. In this case adispersant can be used, and examples of the dispersant include asaponified polyvinyl acetate, modified celluloses such as hydroxyethylcellulose and hydroxypropyl cellulose, and compounds containing an OHgroup such as polyacrylic acid and polymethacrylic acid. In addition,compounds which are used in a usual aqueous suspension polymerizationcan also be widely employed.

The reaction may be carried out by suspending the polymer, thewater-insoluble radical polymerizable monomer, the water-insolubleradical initiator and/or the dispersant in water, and then heating themixture. Here, a ratio of water to the sum of the radical polymerizablemonomer (i.e., the functional group) and the PP copolymer is preferably1:0.1 to 1:200, more preferably 1:1 to 1:100. The heating temperature issuch that the half-life of the radical initiator is preferably from 0.1to 100 hours, more preferably from 0.2 to 10 hours, and it is preferablyfrom 30° to 200° C., more preferably from 40° to 150° C. In the heatingstep, it is preferred that the mixture is stirred sufficiently so as tobecome in a suspension state. In this way, the graft polymer (i.e., thefunctionalized component) may be obtained in granular form.

A weight ratio of the water-insoluble monomer to the polymer maypreferably be from 1:01 to 1:10000, and a weight ratio of the radicalinitiator to the water-insoluble monomer may be from 0.00001 to 0.1. Theratio of the water-insoluble monomer in the functionalized componentdepends upon its use, but the amount of the monomer may be from 0.1 to200% by weight based on the weight of the graft copolymer.

The obtained functionalized component preferably contains a desiredamount of radical polymerizable functional group units in the range offrom 0.1 to 50 wt % based on the weight of the polymer in compliancewith its use or application. When the content of the radicalpolymerizable functional group units is in excess of 50 wt %, theparticular polymer may not exert intrinsic physical properties, and whenit is less than the above-mentioned lower limit, the physical propertiesas the graft copolymer may not be obtained.

Furthermore, a compatibilizing effect within the inventive compositionobtained by inclusion of the functionalized component may be influencedby the level of grafting. In an embodiment, the polymer, copolymer,oligomer, etc. may be functionalized (e.g., grafted) to include about0.001 wt % or greater of the functional group attached and/orincorporated into the polymer backbone. The polymer may also befunctionalized grafted to a higher degree. The level offunctionalization (e.g., the grafting level) may be less than about 50wt %, preferably less than about 45 wt %, preferably less than about 40wt %, preferably less than about 35 wt %, preferably less than about 30wt %, preferably less than about 25 wt %, preferably less than about 20wt %, preferably less than about 15 wt %, preferably less than about 10wt %, preferably less than about 9 wt %, preferably less than about 8 wt%, preferably less than about 7 wt %, preferably less than about 6 wt %,preferably less than about 5 wt %, preferably less than about 4 wt %,preferably less than about 3 wt %, preferably less than about 2 wt %,preferably less than about 1.5 wt %, preferably less than about 1 wt %,preferably less than about 0.5 wt %.

In a preferred embodiment, the blend comprises POA and a functionalizedsyndiotactic rich C3-C40 homopolymer, still more preferably thecomposition comprises a copolymer or homopolymer comprisingfunctionalized syndiotactic rich polypropylene (srPP).

For simplicity, syndiotactic rich polymers may also be referred toherein simply as syndiotactic polymers. Syndiotactic polymers suitablefor use herein comprise a unique stereochemical structure in whichmonomeric units having enantiomorphic configuration of the asymmetricalcarbon atoms follow each other alternately and regularly in themacromolecular main chain. Examples of syndiotactic polypropyleneinclude those described in U.S. Pat. No. 3,258,455, which were obtainedby using a catalyst prepared from titanium trichloride and diethylaluminum monochloride. U.S. Pat. No. 3,305,538, is directed to vanadiumtriacetylacetonate or halogenated vanadium compounds in combination withorganic aluminum compounds for producing syndiotactic polypropylene.U.S. Pat. No. 3,364,190 is directed to a catalyst system composed offinely divided titanium or vanadium trichloride, aluminum chloride, atrialkyl aluminum and a phosphorus-containing Lewis base for producingsyndiotactic polypropylene.

The structure and properties of syndiotactic polypropylene differsignificantly from those of isotactic polypropylene. The isotacticstructure is typically described as having long sequences of monomerunits with the same relative configuration of the tertiary carbon atoms.Using the Fischer projection formula, the stereochemical sequence ofisotactic polypropylene is described as follows:

The methyl groups attached to the tertiary carbon atoms of successivemonomeric units on the same side of a hypothetical plane through themain chain of the polymer, e.g., the methyl groups are all above orbelow the plane. Another way of describing the structure is through theuse of NMR, wherein an isotactic pentad is . . . mmmmm . . . with each“m” representing a “meso” dyad or successive methyl groups on the sameside in the plane. Any deviation or inversion in the structure of thechain lowers the degree of isotacticity and thus the crystallinity ofthe polymer.

In contrast to the isotactic structure, syndiotactic polymers are thosein which long sequences of monomer units have an alternating relativeconfiguration of the tertiary carbon atoms. Using the Fischer projectionformula, the structure of a syndiotactic polymer is designated as:

The methyl groups attached to the tertiary carbon atoms of successivemonomeric units in the chain lie on alternate sides of the plane of thepolymer. In NMR nomenclature, this pentad is described as . . . rrrrr .. . in which each “r” represents a “racemic” dyad, i.e., successivemethyl groups on alternate side of the plane. The percentage of r dyadsin the chain determines the degree of syndiotacticity of the polymer.Syndiotactic polymers may be crystalline and may be similar to isotacticpolymers in that they may be insoluble in xylene. This crystallinitydistinguishes both syndiotactic and isotactic polymers from atacticpolymer, which may be soluble in xylene. Atactic polymer exhibits noregular order of repeating unit configurations in the polymer chain andmay thus form a waxy product.

Preparation and Composition of Syndiotactic Polymers

Catalyst capable of producing syndiotactic rich polypropylene includethose disclosed in U.S. Pat. Nos. 5,476,914, 6,184,326, 6,245,870,5,373,059, 5,374,685, and 5,326,824.

In addition to propylene, the syndiotactic enriched polymer may includeother alpha olefins within the base polymer, including ethylene (C₂) andfrom C₄ to C₄₀. Examples of alpha olefins include butene-1, pentene-1,hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1,dodecene-1, tridecene-1, penetdecene-1, hexadecene-1, heptadecene-1,octadecene-1, and branched olefins including3-methylbutene-1,4-methylepentene-1, and 4,4-dimethylepentene-1. Theamount of the other alpha olefins, when present, may be greater thanabout 0.001% by weight (wt %), based on the total weight of the polymer.Preferably, the amount of the other alpha olefins is greater than orequal to about 0.1 wt %, more preferably greater than or equal to about1 wt %. The other alpha olefins may also be present in the base polymerabout 50 wt % or less. Preferably, the amount of the other alpha olefinsis less than or equal to about 20 wt %, more preferably less than orequal to about 10 wt %.

Syndiotactic rich polypropylene, (srPP) polymers, as defined herein,comprise at least about 50% [r] dyads. Preferably at least about 55% [r]dyads, with at least about 60% [r] dyads preferred, with at least about65% [r] dyads more preferred, with at least about 70% [r] dyads morepreferred, with at least about 75% [r] dyads more preferred, with atleast about 80% [r] dyads yet more preferred, with at least about 85%[r] dyads still more preferred, with at least about 90% [r] dyads stillmore preferred, with at least about 95% [r] dyads yet still morepreferred.

Syndiotactic rich polypropylene may also comprise less than about 55%[r] dyads. Preferably less than about 60% [r] dyads, with less thanabout 65% [r] dyads preferred, with less than about 70% [r] dyads morepreferred, with less than about 75% [r] dyads more preferred, with lessthan about 80% [r] dyads more preferred, with less than about 85% [r]dyads yet more preferred, with less than about 90% [r] dyads still morepreferred, with less than about 92% [r] dyads still more preferred, withless than about 99% [r] dyads yet still more preferred.

In a preferred embodiment, syndiotactic rich polypropylenes may bedefined as polypropylene containing about 58 to 75% [r] dyads, and haveno or very low (e.g., less than about 10%) crystallinity.

In a preferred embodiment the blend comprises POA and functionalizedsrPP. Preferably the srPP is present at 1 to 99 weight %, preferably 2to 85 weight %, preferably 3 to 50 weight %, more preferably 4 to 40weight %, based upon the weight of the blend.

In another embodiment, a master batch of the functionalized polymer isprepared. A preferred mixing ratio between the functionalized componentand a polymer (such as a POA or other homopolymer or copolymer of analpha-olefin) is such that the radical polymerizable functional groupunits, preferably the unsaturated carboxylic acid units in themasterbatch are present in an amount of 0.001 to 50% by weight, based onthe total weight of the polymer and the functionalized component. In apreferred embodiment, the functional groups in the functionalizedcomponent (preferably functionalized propylene homopolymer or copolymer,preferably srPP), may be about 0.01 wt % or greater, preferably about0.1 wt % or greater, preferably about 0.5 wt % or greater, preferablyabout 1 wt % or greater, preferably about 5 wt % or greater, preferablyabout 10 wt % or greater, preferably about 15 wt % or greater,preferably about 20 wt % or greater, about 30 wt % or greater,preferably about 40 wt % or greater, based on the total weight of thefunctionalized propylene homopolymer or copolymer. Preferably, thefunctional group in the functionalized propylene homopolymer orcopolymer, preferably srPP, is about 45 wt % or less, preferably about35 wt % or less, preferably about 25 wt % or less, preferably about 20wt % or less, preferably about 15 wt % or less, preferably about 10 wt %or less, preferably about 5 wt % or less, preferably about 1 wt % orless, based on the total weight of the functionalized propylenehomopolymer or copolymer.

In the process utilized for producing the functionalized propylenehomopolymer or copolymer, no particular restriction need be put on amixing manner, accordingly, the raw materials may be mixed uniformly bymeans of a Henschel mixer or the like and then may be melted, mixed andmolded into pellets by an extruder or the like. It is also possible toutilize a Brabender by which mixing and melting are carried outsimultaneously, and after the melting, the material can be directlymolded into films, sheets, or the like.

Functionalized Propylene Copolymers

In another embodiment the functionalized component comprises one or morefunctionalized polypropylene copolymers derived from propylenecopolymers having elastic properties. Such preferred functionalizedpropylene copolymers may be prepared according the procedures in WO02/36651 which is incorporated by reference here. Likewise the polymersdescribed in WO 03/040202, WO 03/040095, WO 03/040201, WO 03/040233, WO03/040442 may be functionalized as described herein and used in thepractice of this invention. Additionally the polymers described in EP1,233,191, U.S. Pat. No. 6,525,157 may be functionalized as describedherein and used in the practice of this invention.

Preferred propylene copolymers to be functionalized and used hereininclude those prepared by polymerizing propylene with a C₂ or C₄-C₂₀alpha olefin, most preferably propylene and ethylene in the presence ofa chiral metallocene catalyst with an activator and optionally ascavenger. The co-monomer used with propylene may be linear or branched.Preferred linear alpha-olefins include ethylene (C₂) and C₄ to C₈ alphaolefins. Examples of preferred a-olefins include ethylene, 1-butene,1-hexene, and 1-octene, even more preferably ethylene or 1-butene.Preferred branched α-olefins include 4-methyl-1-pentene,3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene.

Preferred propylene copolymers to be functionalized and used hereininclude propylene copolymers may have an average propylene content on amolar basis of from about 68% to about 92%, more preferably from about75% to about 91%, even more preferably from about 78% to about 88%, mostpreferably from about 80% to about 88%. The balance of the copolymer maybe one or more α-olefins as specified above and optionally minor amountsof one or more diene monomers. Preferably, the polypropylene copolymercomprises ethylene as the comonomer in the range of from about 8 to 32mole % ethylene, more preferably from about 9 to about 25 mole %ethylene, even more preferably from about 12 to about 22 mole % ethyleneand most preferably from about 13 to 20 mole % ethylene.

The use of a chiral metallocene catalyst ensures that the methyl groupof the propylene residues have predominantly the same tacticity. Bothsyndiotactic and isotactic configuration of the propylene are possiblethough the isotactic polymers are preferred. The tacticity of thepropylene residues leads to crystallinity in the polymers. For thepolymers of the present invention the low levels of crystallinity in thepolypropylene copolymer are derived from isotactic polypropyleneobtained by incorporating alpha-olefin co-monomers as described above.Preferred propylene copolymers to be functionalized and used hereininclude semi-crystalline propylene copolymers preferably having:

-   -   1. a heat of fusion from about 0.5 J/g to about 25 J/g, more        preferably from about 1 J/g to about 20 J/g, and most preferably        from about 1 J/g to about 15 J/g; and/or    -   2. a crystallinity of about 0.25% to about 15%, more preferably        from about 0.5% to about 13%, and most preferably from about        0.5% to about 11% (The crystallinity of the polypropylene        copolymer is expressed in terms of percentage of crystallinity.        The thermal energy for the highest order of polypropylene is        estimated at 189 J/g. That is, 100% crystallinity is equal to        189 J/g.); and/or    -   3. a single broad melting point or melting transition (A sample        of the polypropylene copolymer may show a secondary melting peak        or peaks adjacent to a principal peak, yet for the purposes        herein, these are considered together as a single melting point        or melting transition.); and or    -   4. a melting point of from about 25° C. to about 75° C.,        preferably in the range of from about 25° C. to about 65° C.,        more preferably in the range of from about 30° C. to about        60° C. (The highest of melting transition peaks is considered        the melting point.); and/or    -   5. a weight average molecular weight, prior to        functionalization, of 10,000 to 5,000,000 g/cc, preferably        80,000 to 500,000; and/or    -   6. an MWD (M_(w)/M_(n)) between 1.5 to 40.0, more preferably        between about 1.8 to 5 and most preferably between 1.8 to 3;        and/or    -   7. a Mooney viscosity ML (1+4)@125° C. less than 100, more        preferably less than 75, even more preferably less than 60, most        preferably less than 30.

In another embodiment, prior to functionalization, preferred propylenecopolymer preferably comprises a random crystallizable copolymer havinga narrow compositional distribution. The intermolecular compositiondistribution of the polymer, may be determined by thermal fractionationin a solvent such as a saturated hydrocarbon e.g., hexane or heptane.This thermal fractionation procedure is described below. By having anarrow compositional distribution, it is meant that approximately 75% byweight and more preferably 85% by weight of the polymer is isolated asone or two adjacent, soluble fraction with the balance of the polymer inimmediately preceding or succeeding fractions. Thus in a copolymerhaving a narrow compositional distribution, each of these fractions mayhave a composition (wt. % ethylene content) with a difference of nogreater than 20% (relative to each other) and more preferably 10%(relative to each other) of the average weight % ethylene content of thepolypropylene copolymer.

The length and distribution of stereoregular propylene sequences inpreferred polypropylene copolymers is consistent with substantiallyrandom statistical copolymerization. It is well known that sequencelength and distribution are related to the copolymerization reactivityratios. By substantially random, we mean copolymer for which the productof the reactivity ratios is generally 2 or less. In stereoblockstructures, the average length of polypropylene sequences is greaterthan that of substantially random copolymers with a similar composition.Prior art polymers with stereoblock structure have a distribution ofpolypropylene sequences consistent with these blocky structures ratherthan a random substantially statistical distribution. The reactivityratios and sequence distribution of the polymer may be determined by ¹³CNMR, as is discussed in detail below, which locates the ethyleneresidues in relation to the neighboring propylene residues. To produce acrystallizable copolymer with the required randomness and narrowcomposition distribution, it is desirable to use (1) a single sitedcatalyst and (2) a well-mixed, continuous flow stirred tankpolymerization reactor which allows only a single polymerizationenvironment for substantially all of the polymer chains of preferredpolypropylene copolymers.

Preferred propylene copolymers to be functionalized and used herein aredescribed in detail as the “Second Polymer Component (SPC)” in U.S.applications U.S. Ser. No. 60/133,966, filed May 13, 1999, and U.S. Ser.No. 60/342,854, filed Jun. 29, 1999, and described in further detail asthe “Propylene Olefin Copolymer” in U.S. Ser. No. 90/346,460, filed Jul.1, 1999, which are both fully incorporated by reference herein forpurposes of U.S. practice.

IN another preferred embodiment, the polymer to be functionalizedcomprises propylene, one or more comonomers (such as ethylene,alpha-olefins having 4 to 8 carbon atoms, and styrenes) and optionallyone or more α, ω dienes. The amount of diene is preferably no greaterthan about 10 wt %, more preferably no greater than about 5 wt %.Preferred dienes include those used for vulcanization of ethylenepropylene rubbers, preferably ethylidene norbornene, vinyl norbornene,dicyclopentadiene, and 1,4-hexadiene (available from DuPont Chemicals).

In another embodiment, the polypropylene copolymer prior tofunctionalization may be a blend of discrete polymers. Such blends mayinclude two or more polypropylene—polyethylene copolymers (as describedabove), two or more polypropylene copolymers (as described above), or atleast one of each such polyethylene copolymer and polypropylenecopolymer, where each of the components of the polymer blend wouldindividually qualify as a polymer component.

It is understood in the context of the present invention that, in oneembodiment, more than one polymer component may be used in a singleblend. Each of the polymer components is described above and the numberof polymer components in this embodiment is less than three and morepreferably, two. In this embodiment of the invention the polymercomponents differ in the α-olefin content with one being in the range of7 to 13 mole % olefin while the other is in the range of 14 to 22 mole %olefin. The preferred olefin is ethylene. It is believed that the use oftwo-polymer components leads to beneficial improvements in thetensile-elongation properties of the blends.

In another embodiment the polymer to be functionalized comprises randomcopolymers (RCP) and or impact copolymers (ICP) also called heterophasiccopolymers or block copolymers. RCPs are usually produced bycopolymerizing in a single reactor process propylene with other monomerssuch as ethylene, butene and higher alpha-olefins, the most common onebeing ethylene. Typical ethylene content for these copolymers range from3-4 mole % up to 14-17 mole %. In a preferred embodiment, propylenepolymers to be functionalized and used herein have an isotactic indexand triad tacticity determined as follows:

Triad Tacticity

The term “tacticity” refers to the stereogenicity in a polymer. Forexample, the chirality of adjacent monomers can be of either like oropposite configuration. The term “diad” is used to designate twocontiguous monomers; three adjacent monomers are called a triad. If thechirality of adjacent monomers is of the same relative configuration,the diad is called isotactic; if opposite in configuration, it is termedsyndiotactic. Another way to describe the configurational relationshipis to term contiguous pairs of monomers having the same chirality asmeso (m) and those of opposite configuration racemic (r).

When three adjacent monomers are of the same configuration, thestereoregularity of the triad is ‘mm’. If two adjacent monomers in athree-monomer sequence have the same chirality and that is differentfrom the relative configuration of the third unit, this triad has ‘mrtacticity. An ‘a’ triad has the middle monomer unit having an oppositeconfiguration from either neighbor. The fraction of each type of triadin the polymer can be determined and when multiplied by 100 indicatesthe percentage of that type found in the polymer.

As indicated above, the reactivity ratios and sequence distribution ofthe polymer may be determined by ¹³C NMR, which locates the ethyleneresidues in relation to the neighboring propylene residues. The triadtacticity can be determined from a ¹³C NMR spectrum of the propylenecopolymer. The ¹³C NMR spectrum is measured in the following manner.

To measure the ¹³C NMR spectrum, 250-350 mg of the copolymer iscompletely dissolved in deuterated tetrachloroethane in a NMR sampletube (diameter: 10 mm) at 120° C. The measurement is conducted with fullproton decoupling using a 90° pulse angle and at least a 15 second delaybetween pulses.

With respect to measuring the chemical shifts of the resonances, themethyl group of the third unit in a sequence of 5 contiguous propyleneunits consisting of head-to-tail bonds and having the same relativechirality is set to 21.83 ppm. The chemical shift of other carbonresonances are determined by using the above-mentioned value as areference. The spectrum relating to the methyl carbon region (17.0-23ppm) can be classified into the first region (21.1-21.9 ppm), the secondregion (20.4-21.0 ppm), the third region (19.5-20.4 ppm) and the fourthregion (17.0-17.5 ppm). Each peak in the spectrum was assigned withreference to literature source such as the articles in, “Polymer” 30(1989) 1350 or “Macromolecules”, 17 (1984) 1950 which are frillyincorporated by reference.

In the first region, the signal of the center methyl group in a PPP (mm)triad is located.

In the second region, the signal of the center methyl group in a PPP(mr) triad and the methyl group of a propylene unit whose adjacent unitsare a propylene unit and an ethylene unit resonates (PPE-methyl group).

In the third region, the signal of the center methyl group in a PPP (a)triad and the methyl group of a propylene unit whose adjacent units areethylene units resonate (EPE-methyl group).

PPP (mm), PPP (mr) and PPP (a) have the following three-propyleneunits-chain structure with head-to-tail bonds, respectively. This isshown in the Fischer projection diagrams below.

The triad tacticity (mm fraction) of the propylene copolymer can bedetermined from a ¹³C-NMR spectrum of the propylene copolymer and thefollowing formula:

${m\; m\mspace{14mu}{Fraction}} = \frac{{PPP}\mspace{14mu}\left( {m\; m} \right)}{{{PPP}\mspace{14mu}\left( {m\; m} \right)} + {{PPP}({mr})} + {{PPP}({rr})}}$

The peak areas used in the above calculation are not measured directlyfrom the triad regions in the ¹³C-NMR spectrum. The intensities of themr and a triad regions need to have subtracted from them the areas dueto EPP and EPE sequencing, respectively. The EPP area can be determinedfrom the signal at 30.8 ppm after subtracting from it one half the areaof the sum of the signals between 26 and 27.2 ppm and the signal at 30.1ppm. The area due to EPE can be determined from the signal at 33.2 ppm.

In addition to the above adjustments to the mr and rr regions for thepresence of EPP and EPE, other adjustments need to be made to theseregions prior to using the above formula. These adjustments are neededto account for signals present due to non-head-to-tail propyleneadditions. The area of the mr region may be adjusted by subtracting onehalf of the area between 34 and 36 ppm and the area of the rr region maybe adjusted by subtracting the intensity found between 33.7 and 40.0ppm. Therefore, by making the above adjustments to the mr and rr regionsthe signal intensities of the mm, mr and rr triads can be determined andthe above formula applied.

Preferred propylene ethylene copolymers useful in this invention haveunique propylene tacticity as measured by % meso triad. As shown indetail in U.S. Ser. No. 09/108,772, filed Jul. 1, 1998, fullyincorporated herein by reference, the copolymers have a lower % mesotriad for any given ethylene content when compared to U.S. Pat. No.5,504,172. The lower content of % meso triads corresponds to relativelylower crystallinity that translates into better elastomeric propertiessuch as high tensile strength and elongation at break coupled with verygood elastic recovery.

In another embodiment, preferred polylefins to be functionalized andused herein include those described in WO 02/083753. Preferably thepolyolefins is a copolymer comprising 5 to 25% by weight ofethylene-derived units and 95 to 75% by weight of propylene-derivedunits, the copolymer having:

-   -   (a) a melting point of less than 90° C.;    -   (b) a relationship of elasticity to 500% tensile modulus such        that        Elasticity≦0.935M+12,    -    where elasticity is in percent and M is the 500% tensile        modulus in MPa; and    -   (c) a relationship of flexural modulus to 500% tensile modulus        such that        Flexural Modulus≦4.2e^(0.27M)+50,    -    where flexural modulus is in MPa and M is the 500% tensile        modulus in MPa, here tensile modulus and flexural modulus are        determined as stated in WO 02/083753.

The functionalized component may be mixed or blended with (i.e., incombination with, an admixture of, and the like) POA having no graftcomponent, a different graft component, or a similar graft component ata different level of inclusion, and/or the like, to achieve a finaladhesive composition with a desired level of adhesion for a particularend use or process.

In an embodiment, in addition to the propylene copolymer, thefunctionalized component may also include an alpha-olefin homopolymer orcopolymer containing no graft component. If desired, the alpha-olefinhomopolymers may have various molecular weight characteristics, may berandom and/or block copolymers of alpha-olefins themselves. Examples ofthe alpha-olefin include ethylene and alpha-olefins having 4 to 20carbon atoms in addition to propylene. The homopolymers and copolymersof these alpha-olefins can be manufactured by various known methods, andmay be commercially available under various trade names.

In the process utilized for producing the functionalized components andthe final blends, no particular restriction need be put on a mixingmanner, accordingly, the raw materials may be mixed uniformly by meansof a Henschel mixer or the like and then may be melted, mixed and moldedinto pellets by an extruder or the like. It is also possible to utilizea Brabender mixer by which mixing and melting are carried outsimultaneously, and after the melting, the material can be directlymolded into films, sheets, or the like. Thus, the blends describedherein may be formed using conventional techniques known in the art suchthat blending may be accomplished using one or more static mixers,in-line mixers, elbows, orifices, baffles, or any combination thereof.

In a preferred embodiment the POA and the functionallized component arecombined in a weight to weight ratio of POA to functionalized componentin the range of about 1:1000 to 1000:1. Preferably the weight to weightratio may be about 1:100, about 1:50, about 1:20, about 1:10, about 1:5,about 1:4, about 1:3, about 1:2, or about 1:1. Alternately, the weightto weight ratio may be about 100:1, about 50:1, about 20:1, about 10:1,about 5:1, about 4:1, about 3:1, or about 2:1.

Formulations

The composition comprising the admixture of components 1 and 2, asproduced herein, may be used directly as an adhesive, or may be blended,mixed and/or combined with other components to form an adhesiveformulation.

Tackifiers may be used with the compositions of the present invention.Examples of suitable tackifiers, include, but are not limited to,aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbonresins, hydrogenated polycyclopentadiene resins, polycyclopentadieneresins, gum rosins, gum rosin esters, wood rosins, wood rosin esters,tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modifiedpolyterpenes, terpene phenolics, aromatic modified hydrogenatedpolycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenatedaliphatic aromatic resins, hydrogenated terpenes and modified terpenes,hydrogenated rosin acids, and hydrogenated rosin esters. In someembodiments the tackifier may be hydrogenated.

In other embodiments, the tackifier may be non-polar. (Non-polar meaningthat the tackifier is substantially free of monomers having polargroups. Preferably, the polar groups are not present, however if theyare present, they are preferably not present at more that 5 weight %,preferably not more that 2 weight %, even more preferably no more than0.5 weight %.) In some embodiments the tackifier may have a softeningpoint (Ring and Ball, as measured by ASTM E-28) of 80° C. to 150° C.,preferably 100° C. to 130° C. In another embodiment the resins is liquidand has a R and B softening point of between 10 and 70° C.

The tackifier, if present in the composition, may comprise about 1 toabout 80 weight %, based upon the weight of the composition, morepreferably 2 to 40 weight %, even more preferably 3 to 30 weight %.

Preferred hydrocarbon resins for use as tackifiers or modifiers include:

-   -   1. Resins such as C₅/C₆ terpene resins, styrene terpenes,        alpha-methyl styrene terpene resins, C₉ terpene resins, aromatic        modified C₅/C₆, aromatic modified cyclic resins, aromatic        modified dicyclopentadiene based resins or mixtures thereof.        Additional preferred resins include those described in WO        91/07472, U.S. Pat. Nos. 5,571,867, 5,171,793 and 4,078,132.        Typically these resins are obtained from the cationic        polymerization of compositions containing one or more of the        following monomers: C₅ diolefins (such as 1-3 pentadiene,        isoprene, and the like); C₅ olefins (such as 2-methylbutenes,        cyclopentene, and the like); C₆ olefins (such as hexene), C₉        vinylaromatics (such as styrene, alpha methyl styrene,        vinyltoluene, indene, methyl indene, and the like); cyclics        (such as dicyclopentadiene, methyldicyclopentadiene, and the        like); and or terpenes (such as limonene, carene, thujone, and        the like).    -   2. Resins obtained by the thermal polymerization of        dicyclopentadiene, and/or the thermal polymerization of dimers        or oligomers of cyclopentadiene and/or methylcyclopentadiene,        optionally with vinylaromatics (such as styrene, alpha-methyl        styrene, vinyl toluene, indene, methyl indene, and the like).

The resins obtained after polymerization and separation of unreactedmaterials, can be hydrogenated if desired. Examples of preferred resinsinclude those described in U.S. Pat. No. 4,078,132; WO 91/07472; U.S.Pat. No. 4,994,516; EP 0 046 344 A; EP 0 082 726 A; and U.S. Pat. No.5,171,793.

Crosslinking Agents

In another embodiment an adhesive composition comprising polymer productof this invention may further comprises a crosslinking agent. Preferredcrosslinking agents include those having functional groups that canreact with the acid or anhydride group. Preferred crosslinking agentsinclude alcohols, multiols, amines, diamines and/or triamines.Particular examples of crosslinking agents useful in this inventioninclude polyamines such as ethylenediamine, diethylenetriamine,hexamethylenediamine, diethylaminopropylamine, and/or menthanediamine.

In another embodiment, the composition of this invention comprises oneor more phenolic antioxidants. Preferred examples of a phenolicantioxidants include a substituted phenol such as 2,6-di-t-butylphenolin which a hydrogen atom at 2 and/or 6 position is substituted by analkyl residue. Typical examples of the phenolic antioxidant include2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, vitamin E,2-t-butyl-6-(3′-t-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenylacrylate, 2,2′-methylene-bis(4-methyl-6-t-butylphenyl),2,2′-methylene-bis(4-ethyl-6-t-butyl-phenol),2,2′-methylene-bis(6-cyclohexyl-4-methylphenol),1,6-hexanediol-bis([3-(3,5-di-t-butyl[4-hydroxyphenyl])]propionate andpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate.

The amount of each of these additives to be added is such that theweight ratio of the additive to the functionalized propylene homopolymerof copolymer is preferably 1/1000 to 1/100000, more preferably 1/500 to1/10000.

To the above-mentioned composition, there can be added a neutralizingagent such as calcium stearate, magnesium hydroxide, aluminum hydroxideor hydrotalcite, and a nucleating agent such as a salt of benzoic acid,sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate and benzylsorbitol, and the like, in addition to the above-mentioned stabilizer.

Additives

In another embodiment, an adhesive composition of this invention furthercomprises typical additives known in the art such as fillers,antioxidants, adjuvants, adhesion promoters, oils, and/or plasticizers.Preferred fillers include titanium dioxide, calcium carbonate, bariumsulfate, silica, silicon dioxide, carbon black, sand, glass beads,mineral aggregates, talc, clay and the like. Preferred antioxidantsinclude phenolic antioxidants, such as Irganox 1010, Irganox, 1076 bothavailable from Ciba-Geigy. Preferred oils include paraffinic ornapthenic oils such as Primol 352, or Primol 876 available fromExxonMobil Chemical France, S.A. in Paris, France. Preferredplasticizers include polybutenes, such as Parapol 950 and Parapol 1300formerly available from ExxonMobil Chemical Company in Houston Tex.Other preferred additives include block, antiblock, pigments, processingaids, UV stabilizers, neutralizers, lubricants, surfactants and/ornucleating agents may also be present in one or more than one layer inthe films. Preferred additives include silicon dioxide, titaniumdioxide, polydimethylsiloxane, talc, dyes, wax, calcium sterate, carbonblack, low molecular weight resins and glass beads. Preferred adhesionpromoters include polar acids, polyaminoamides (such as Versamid 115,125, 140, available from Henkel), urethanes (such as isocyanate/hydroxyterminated polyester systems, e.g. bonding agent TN/Mondur Cb-75(Miles,Inc.), coupling agents, (such as silane esters (Z-6020 from DowCorning)), titanate esters (such as Kr-44 available from Kenrich),reactive acrylate monomers (such as sarbox SB-600 from Sartomer), metalacid salts (such as Saret 633 from Sartomer), polyphenylene oxide,oxidized polyolefins, acid modified polyolefins, and anhydride modifiedpolyolefins.

In another embodiment the adhesive composition may be combined with lessthan 3 wt % anti-oxidant, less than 3 wt % flow improver, less than 10wt % wax, and or less than 3 wt % crystallization aid.

Other optional components that may be combined with the adhesivecomposition as disclosed herein include plasticizers, and/or otheradditives such as oils, surfactants, fillers, color masterbatches, andthe like. Preferred plasticizers include mineral oils, polybutenes,phthalates and the like. Particularly preferred plasticizers includephthalates such as di-iso-undecyl phthalate (DIUP),di-iso-nonylphthalate (DINP), dioctylphthalates (DOP) and/or the like.Particularly preferred oils include aliphatic naphthenic oils.

Other optional components that may be combined with the polymer productof this invention are low molecular weight products such as wax, oil orlow Mn polymer, (low meaning below Mn of 5000, preferably below 4000,more preferably below 3000, even more preferably below 2500). Preferredwaxes include polar or non-polar waxes, polypropylene waxes,polyethylene waxes, and wax modifiers. Preferred waxes include ESCOMER™101. Preferred oils include aliphatic napthenic oils, white oils or thelike. Preferred low Mn polymers include polymers of lower alpha olefinssuch as propylene, butene, pentene, hexene and the like. A particularlypreferred polymer includes polybutene having an Mn of less than 1000. Anexample of such a polymer is available under the trade name PARAPOL™ 950from ExxonMobil Chemical Company. PARAPOL™ 950 is a liquid polybutenepolymer having an Mn of 950 and a kinematic viscosity of 220 cSt at 100°C., as measured by ASTM D 445. In some embodiments the polar andnon-polar waxes are used together in the same composition.

In some embodiments, however, wax may not be desired and is present atless than 5 weight %, preferably less than 3 weight %, more preferablyless than 1 weight %, more preferably less than 0.5 weight %, based uponthe weight of the composition.

In another embodiment the composition of this invention may have lessthan 30 weight % total of any combination of additives described above,preferably less than 25 weight %, preferably less than 20 weight %,preferably less than 15 weight %, preferably less than 10 weight %,preferably less than 5 weight %, based upon the total weight ofcomponent 1 and component 2, and the additives.

In another embodiment, the composition of this invention may be blendedwith elastomers (preferred elastomers include all natural and syntheticrubbers, including those defined in ASTM D1566). In a preferredembodiment, elastomers may be blended with the composition of thepresent invention to form rubber toughened compositions. In aparticularly preferred embodiment, the rubber toughened composition is atwo (or more) phase system where the rubber is a discontinuous phase andthe inventive composition forms the continuous phase. Examples ofpreferred elastomers include one or more of the following: ethylenepropylene rubber, ethylene propylene diene monomer rubber, neoprenerubber, styrenic block copolymer rubbers (including SI, SIS, SB, SBS,SIBS, SEBS, SEPS, and the like (S is styrene, I is isoprene, B isbutadiene, EB is ethylenebutylene, EP is ethylenepropylene), butylrubber, halobutyl rubber, copolymers of isobutylene andpara-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene. This blend may be combined with the tackifiers and/orother additives as described above.

In another embodiment the adhesive composition may be blended withimpact copolymers. Impact copolymers are defined to be a blend ofisotactic PP and an elastomer such as an ethylene-propylene rubber. In apreferred embodiment the blend is a two (or more) phase system where theimpact copolymer is a discontinuous phase and the combination ofcomponent 1 and component 2 as described above, is the continuous phase.

In another embodiment the polymer produced by this invention may beblended with ester polymers. In a preferred embodiment the blend is atwo (or more) phase system where the polyester is a discontinuous phaseand the composition is the continuous phase.

The composition of this invention or formulations thereof may then beapplied directly to a substrate or may be sprayed thereon. Thecomposition may be molten, or heated to a semisolid state prior orduring application. Spraying is defined to include atomizing, such asproducing an even dot pattern, spiral spraying such as NordsonControlled Fiberization or oscillating a stretched filament like may bedone in the ITW Dynafiber/Omega heads or Summit technology from Nordson.The compositions of this invention may also be melt blown. Melt blowntechniques are defined to include the methods described in U.S. Pat. No.5,145,689 or any process where air streams are used to break upfilaments of the extrudate and then used to deposit the broken filamentson a substrate. In general, melt blown techniques are processes that useair to spin hot melt adhesive fibers and convey them onto a substratefor bonding. Fibers sizes can easily be controlled from 20-200 micronsby changing the melt to air ratio. Few, preferably no, stray fibers aregenerated due to the inherent stability of adhesive melt blownapplicators. Under UV light the bonding appears as a regular, smooth,stretched dot pattern. Atomization is a process that uses air to atomizehot melt adhesive into very small dots and convey them onto a substratefor bonding.

Preferred unsaturated acids or anhydrides include any unsaturatedorganic compound containing at least one double bond and at least onecarbonyl group. Representative acids include carboxylic acids,anhydrides, esters and their salts, both metallic and non-metallic.Preferably the organic compound contains an ethylenic unsaturationconjugated with a carbonyl group (—C═O). Examples include maleic,fumaric, acrylic, methacrylic, itaconic, crotonic, alpha.methylcrotonic, and cinnamic acids as well as their anhydrides, esters andsalt derivatives. Particularly preferred functional groups includemaleic acid and maleic anhydride. Maleic anhydride is particularlypreferred. The unsaturated acid or anhydride is preferably present atabout 0.1 weight % to about 10 weight %, preferably at about 0.5 weight% to about 7 weight %, even more preferably at about 1 to about 4 weight%, based upon the weight of the polymer and the unsaturated acid oranhydride. In a preferred embodiment the unsaturated acid or anhydriedcomprises a carboxylic acid or a derivative thereof selected from thegroup consisting of unsaturated carboxylic acids, unsaturated carboxylicacid derivatives selected from esters, imides, amides, anhydrides andcyclic acid anhydrides or mixtures thereof.

Tackifiers

In a preferred embodiment, the adhesives of this invention furthercomprise a tackifier, preferably present at about 1 to about 80 weight%, based upon the weight of the blend, more preferably 2 to 40 weight %,even more preferably 3 to 30 weight %; based upon the weight of theadhesive.

Examples of suitable tackifiers for use in this invention include, butare not limited to, aliphatic hydrocarbon resins, aromatic modifiedaliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins,polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins,wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes,aromatic modified polyterpenes, terpene phenolics, aromatic modifiedhydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin,hydrogenated aliphatic aromatic resins, hydrogenated terpenes andmodified terpenes, hydrogenated rosin acids, and hydrogenated rosinesters. In some embodiments the tackifier is hydrogenated.

In an embodiments the tackifier is non-polar. (Non-polar meaning thatthe tackifier is substantially free of monomers having polar groups.Preferably the polar groups are not present, however if they arepreferably they are not present at more that 5 weight %, preferably notmore that 2 weight %, even more preferably no more than 0.5 weight %.)In some embodiments the tackifier has a softening point (Ring and Ball,as measured by ASTM E-28) of 80° C. to 150° C., preferably 100° C. to130° C. In another embodiment the resins is liquid and has a R and Bsoftening point of between 10 and 70° C.

Preferred hydrocarbon resins for use as tackifiers include:

-   -   1. Resins such as C5/C6 terpene resins, styrene terpenes,        alpha-methyl styrene terpene resins, C9 terpene resins, aromatic        modified C5/C6, aromatic modified cyclic resins, aromatic        modified dicyclopentadiene based resins or mixtures thereof.        Additional preferred resins include those described in WO        91/07472, U.S. Pat. Nos. 5,571,867, 5,171,793 and 4,078,132.        Typically these resins are obtained from the cationic        polymerization of compositions containing one or more of the        following monomers: C5 diolefins (such as 1-3 pentadiene,        isoprene, etc); C5 olefins (such as 2-methylbutenes,        cyclopentene, etc.); C6 olefins (such as hexene), C9        vinylaromatics (such as styrene, alpha methyl styrene,        vinyltoluene, indene, methyl indene, etc.); cyclics (such as        dicyclopentadiene, methyldicyclopentadiene, etc.); and or        terpenes (such as limonene, carene, etc).    -   2. Resins obtained by the thermal polymerization of        dicyclopentadiene, and/or the thermal polymerization of dimers        or oligomers of cyclopentadiene and/or methylcyclopentadiene,        optionally with vinylaromatics (such as styrene, alpha-methyl        styrene, vinyl toluene, indene, methyl indene).

The hydrocarbon resins (tackifiers) obtained after polymerization andseparation of unreacted materials, can be hydrogenated if desired.Examples of preferred resins include those described in U.S. Pat. No.4,078,132; WO 91/07472; U.S. Pat. No. 4,994,516; EP 0 046 344 A; EP 0082 726 A; and U.S. Pat. No. 5,171,793.

The Adhesive Blend

The adhesive blends prepared herein may be prepared by any conventionalblending means known in the art.

In another embodiment the adhesive composition further comprises acrosslinking agent. Preferred crosslinking agents include those havingfunctional groups that can react with the acid or anhydride group.Preferred crosslinking agents include alcohols, multiols, amines,diamines and/or triamines. Examples of crosslinking agents useful inthis invention include polyamines such as ethylenediamine,diethylenetriamine, hexamethylenediamine, diethylaminopropylamine,and/or menthanediamine.

In another embodiment the adhesive composition further comprises typicaladditives known in the art such as fillers, antioxidants, adjuvants,adhesion promoters, oils, plasticizers, block, antiblock, pigments,dyes, processing aids, UV stabilizers, neutralizers, lubricants,surfactants, nucleating agents, synergists, polymeric additives,defoamers, preservatives, thickeners, rheology modifiers, humectants,fillers and/or water,

Preferred fillers include titanium dioxide, calcium carbonate, bariumsulfate, silica, silicon dioxide, carbon black, sand, glass beads,mineral aggregates, talc, clay, and the like.

Preferred antioxidants include phenolic antioxidants, such as Irganox1010, Irganox, 1076 both available from Ciba-Geigy. Particularlypreferred antioxidants include those selected from the group consistingof thioesters, phosphates, hindered phenols, tetrakis (methylene3-(3′,5′-di-t-butyl-4 hydroxyphenyl)propionate)methane,2,2′-ethyldenebis (4,6-di-tertiarybutylphenol), 1,1-3-tris(2-methyl-4-hydroxy-5-t-butylephenyl)butane, 1,3,5-trimethyl2,4,6,tris(3,5-tertbutyl-4-hydroxybenzyl)benzene, dilaurylthiodipropionate,pentaerythritol tetrakis (beta-laurylthiopropionate), alkyl-aryldi- andpolyphosphates, thiophosphites, and combinations or derivatives thereof.Particularly preferred plasticizers include di-iso-undecyl phthalate(DIUP), di-iso-nonylphthalate (DINP), dioctylphthalates (DOP),combinations thereof, or derivatives thereof.

Preferred oils include paraffinic or napthenic oils such as Primol 352,or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris,France. Preferred oils also include aliphatic napthenic oils, white oilsor the like.

Preferred plasticizers include polybutenes, such as Parapol 950 andParapol 1300 formerly available from ExxonMobil Chemical Company inHouston Tex., mineral oils, polybutenes, phthalates and the like.Particularly preferred plasticizers include phthalates such asdi-iso-undecyl phthalate (DIUP), di-iso-nonylphthalate (DINP),dioctylphthalates (DOP) and the like. Particularly preferred oilsinclude aliphatic naphthenic oils.

Preferred adhesion promoters include polar acids, polyaminoamides (suchas Versamid 115, 125, 140, available from Henkel), urethanes (such asisocyanate/hydroxy terminated polyester systems, e.g. bonding agentTN/Mondur Cb-75(Miles, Inc.), coupling agents, (such as silane esters(Z-6020 from Dow Corning)), titanate esters (such as Kr-44 availablefrom Kenrich), reactive acrylate monomers (such as sarbox SB-600 fromSartomer), metal acid salts (such as Saret 633 from Sartomer),polyphenylene oxide, oxidized polyolefins, acid modified polyolefins,and anhydride modified polyolefins.

In an embodiment the adhesive composition comprises less than 3 wt %anti-oxidant, less than 3 wt % flow improver, less than 10 wt % wax, andor less than 3 wt % crystallization aid.

In another embodiment the adhesive composition comprises low molecularweight products such as wax, oil or low Mn polymer, (low meaning belowMn of 5000, preferably below 4000, more preferably below 3000, even morepreferably below 2500). Preferred waxes include polar or non-polarwaxes, polypropylene waxes, polyethylene waxes, and wax modifiers.Preferred waxes include ESCOMER™ 101. Particularly preferred waxes areselected from the group consisting of: polar waxes, non-polar waxes,Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamidewaxes, functionalized waxes, polypropylene waxes, polyethylene waxes,wax modifiers, amorphous waxes, carnauba waxes, castor oil waxes,microcrystalline waxes, beeswax, carnauba wax, castor wax, spermacetiwax, vegetable wax, candelilla wax, japan wax, ouricury wax, douglas-firbark wax, rice-bran wax, jojoba wax, bayberry wax, montan wax, peat wax,ozokerite wax, ceresin wax, petroleum wax, paraffin wax, polyethylenewax, chemically modified hydrocarbon wax, substituted amide wax, andcombinations and derivatives thereof.

Preferred low Mn polymers include polymers of lower alpha olefins suchas propylene, butene, pentene, hexene and the like. A particularlypreferred polymer includes polybutene having an Mn of less than 1000. Anexample of such a polymer is available under the trade name PARAPOL™ 950from ExxonMobil Chemical Company. PARAPOL™ 950 is a liquid polybutenepolymer having an Mn of 950 and a kinematic viscosity of 220 cSt at 100°C., as measured by ASTM D 445. In some embodiments the polar andnon-polar waxes are used together in the same composition.

In some embodiments, however, wax may not be desired and is present atless than 5 weight %, preferably less than 3 weight %, more preferablyless than 1 weight %, more preferably less than 0.5 weight %, based uponthe weight of the composition.

In another embodiment the polymers of this invention have less than 30weight % total of any combination of additives described above,preferably less than 25 weight %, preferably less than 20 weight %,preferably less than 15 weight %, preferably less than 10 weight %,preferably less than 5 weight %, based upon the weight of the polymerand the additives.

In another embodiment the adhesive compositions of this invention areblended with elastomers (preferred elastomers include all natural andsynthetic rubbers, including those defined in ASTM D1566). Examples ofpreferred elastomers include one or more of the following: ethylenepropylene rubber, ethylene propylene diene monomer rubber, neoprenerubber, styrenic block copolymer rubbers (including SI, SIS, SB, SBS,SIBS, SEBS, SEPS, and the like (S is styrene, I is isoprene, B isbutadiene, EB is ethylenebutylene, EP is ethylenepropylene), butylrubber, halobutyl rubber, copolymers of isobutylene andpara-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene. This blend may be combined with the tackifiers and/orother additives as described above.

In another embodiment the adhesive composition produced by thisinvention may be blended with impact copolymers. Impact copolymers aredefined to be a blend of isotactic PP and an elastomer such as anethylene-propylene rubber. In a preferred embodiment the blend is a two(or more) phase system where the impact copolymer is a discontinuousphase and the polymer is a continuous phase.

In another embodiment the adhesive composition produced by thisinvention may be blended with ester polymers. In a preferred embodimentthe blend is a two (or more) phase system where the polyester is adiscontinuous phase and the polymer is a continuous phase.

In a preferred embodiment the adhesive composition is combined withmetallocene polyethylenes (mPE's) or metallocene polypropylenes (mPP's).The mPE and mPP homopolymers or copolymers are typically produced usingmono- or bis-cyclopentadienyl transition metal catalysts in combinationwith an activator of alumoxane and/or a non-coordinating anion insolution, slurry, high pressure or gas phase. The catalyst and activatormay be supported or unsupported and the cyclopentadienyl rings by maysubstituted or unsubstituted. Several commercial products produced withsuch catalyst/activator combinations are commercially available fromExxonMobil Chemical Company in Baytown, Tex. under the tradenamesEXCEED™, ACHIEVE™ and EXACT™. For more information on the methods andcatalysts/activators to produce such mPE homopolymers and copolymers seeWO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. Pat. Nos.5,153,157; 5,198,401; 5,240,894; 5,017,714; CA 1,268,753; U.S. Pat. No.5,324,800; EPA 129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 9200333; U.S. Pat. Nos. 5,096,867; 5,507,475; EPA 426 637; EPA 573 403;EPA 520 732; EPA 495 375; EPA 500 944; EPA 570 982; WO91/09882;WO94/03506 and U.S. Pat. No. 5,055,438.

In another embodiment the adhesive composition are blended with ahomopolymer and/or copolymer, including but not limited to,homopolypropylene, propylene copolymerized with up to 50 weight % ofethylene or a C4 to C20 alpha.-olefin, isotactic polypropylene, highlyisotactic polypropylene, syndiotactic polypropylene, random copolymer ofpropylene and ethylene and/or butene and/or hexene, polybutene, ethylenevinyl acetate, low density polyethylene (density 0.915 to less than0.935 g/cm³) linear low density polyethylene, ultra low densitypolyethylene (density 0.86 to less than 0.90 g/cm³), very low densitypolyethylene (density 0.90 to less than 0.915 g/cm³), medium densitypolyethylene (density 0.935 to less than 0.945 g/cm³), high densitypolyethylene (density 0.945 to 0.98 g/cm³), ethylene vinyl acetate,ethylene methyl acrylate, copolymers of acrylic acid,polymethylmethacrylate or any other polymers polymerizable by ahigh-pressure free radical process, polyvinylchloride, polybutene-1,isotactic polybutene, ABS resins, elastomers such as ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer elastomers such asSBS, nylons (polyamides), polycarbonates, PET resins, crosslinkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, high molecularweight polyethylene having a density of 0.94 to 0.98 g/cm³ low molecularweight polyethylene having a density of 0.94 to 0.98 g/cm³, graftcopolymers generally, polyacrylonitrile homopolymer or copolymers,thermoplastic polyamides, polyacetal, polyvinylidine fluoride and otherfluorinated elastomers, polyethylene glycols and polyisobutylene.

In a preferred embodiment the adhesive composition of this invention ispresent in the blend (of adhesive composition and one or more polymers)at from 10 to 99 weight %, based upon the weight of the adhesivecomposition and the polymers in the blend, preferably 20 to 95 weight %,even more preferably at least 30 to 90 weight %, even more preferably atleast 40 to 90 weight %, even more preferably at least 50 to 90 weight%, even more preferably at least 60 to 90 weight %, even more preferablyat least 70 to 90 weight %.

Properties of the Adhesive Composition

The adhesive compositions prepared herein preferably show substratefiber tear at −10° C. when the adhesive is applied to 56 pound virginhigh performance parerboard stock (available from Inland Paper, RomeGa.), preferably at least 5%, more preferably at least 10%, morepreferably at least 20%, more preferably at least 30%, more preferablyat least 40%, more preferably at least 50%, more preferably at least60%, more preferably at least 70%, more preferably at least 80%, morepreferably at least 90%, more preferably 100%.

In another embodiment the adhesive prepared herein has a viscosity (alsoreferred to a Brookfield Viscosity or Melt Viscosity) of 90,000 mPa·secor less at 190° C. (as measured by ASTM D 3236 at 190° C.; ASTM=AmericanSociety for Testing and Materials); or 80,000 or less, or 70,000 orless, or 60,000 or less, or 50,000 or less, or 40,000 or less, or 30,000or less, or 20,000 or less, or 10,000 or less, or 8,000 or less, or 5000or less, or 4000 or less, or 3000 or less, or 1500 or less, or between250 and 6000 mPa·sec, or between 500 and 5500 mPa·sec, or between 500and 3000 mPa·sec, or between 500 and 1500 mPa·sec, and/or a viscosity of8000 mPa·sec or less at 160° C. (as measured by ASTM D 3236 at 160° C.);or 7000 or less, or 6000 or less, or 5000 or less, or 4000 or less, or3000 or less, or 1500 or less, or between 250 and 6000 mPa·sec, orbetween 500 and 5500 mPa·sec, or between 500 and 3000 mPa·sec, orbetween 500 and 1500 mPa·sec. In other embodiments the viscosity is200,000 mPa·sec or less at 190° C., depending on the application. Inother embodiments the viscosity is 50,000 mPa·sec or less depending onthe applications.

In another embodiment the adhesive composition prepared herein has aheat of fusion of 70 J/g or less, or 60 J/g or less, or 50 J/g or less;or 40 J/g or less, or 30 J/g or less, or 20 J/g or less and greater thanzero, or greater than 1 J/g, or greater than 10 J/g, or between 20 and50 J/g.

In another embodiment the adhesive composition prepared herein also hasa Shore A Hardness (as measured by ASTM 2240) of 95 or less, 70 or less,or 60 or less, or 50 or less, or 40 or less or 30 or less, or 20 orless. In other embodiments the Shore A Hardness is 5 or more, 10 ormore, or 15 or more. In certain applications, such as packaging, theShore A Hardness is preferably 50-85. In another embodiment, the polymerhas a Shore A hardness of 20-90.

In another embodiment the adhesive composition prepared herein has aShear Adhesion Fail Temperature (SAFT—as measured by ASTM 4498) of 200°C. or less, or of 40 to 150° C., or 60 to 130° C., or 65 to 110° C., or70-80° C. In certain embodiments SAFT's of 130-140° C. are preferred. Inother embodiments, SAFT's of 100-130° C. are preferred. In otherembodiments, SAFT's of 110-140° C. are preferred.

In another embodiment the adhesive composition prepared herein also hasa Dot T-Peel on Kraft paper of between 1 Newton and 10,000 Newtons, or 3and 4000 Newtons, or between 5 and 3000 Newtons, or between 10 and 2000Newtons, or between 15 and 1000 Newtons. Dot T-Peel is determinedaccording to ASTM D 1876, as described below.

In another embodiment the adhesive composition prepared herein has a settime of several days to 1 second, or 60 seconds or less, or 30 secondsor less, or 20 seconds or less, or 15 seconds or less, or 10 seconds orless, or 5 seconds or less, or 4 seconds or less, or 3 seconds or less,or 2 seconds or less, or 1 second or less.

In another embodiment the adhesive composition prepared herein has astrain at break (as measured by ASTM D-1708 at 25° C.) of 50 to 1000%,preferably 80 to 200%. In some other embodiments the strain at break is100 to 500%.

In another embodiment, the adhesive composition prepared herein has atensile strength at break (as measured by ASTM D-1708 at 25° C.) of 0.5MPa or more, alternatively 0.75 MPa or more, alternatively 1.0 MPa ormore, alternatively 1.5 MPa or more, alternatively 2.0 MPa or more,alternatively 2.5 MPa or more, alternatively 3.0 MPa or more,alternatively 3.5 MPa or more.

In another embodiment the adhesive compositions prepared herein have acloud point of 200° C. or less, preferably 180° C. or less, preferably160° C. or less, preferably 120° C. or less, preferably 100° C. or less.Likewise any composition that the POA is part of preferably has a cloudpoint of 200° C. or less, preferably 180° C. or less, preferably 160° C.or less, preferably 120° C. or less, preferably 100° C. or less.

In another embodiment the adhesive compositions prepared herein have aPeel Strength on MYLAR at 25° C. of and a separation speed of 5 cm perminute of 0.05 lb/in or more, preferably 1 lb/in or more, preferably 5lb/in for more, preferably 10 lb/in or more.

In another embodiment the adhesive compositions prepared herein have aPeel Strength on polypropylene at 25° C. of and a separation speed of 5cm per minute of 0.05 lb/in or more, preferably 1 lb/in or more,preferably 5 lb/in for more, preferably 10 lb/in or more.

In another embodiment the adhesive compositions prepared herein have aPeel Strength on propylene at −10° C. of and a separation speed of 5 cmper minute of 0.05 lb/in or more, preferably 1 lb/in or more, preferably5 lb/in for more, preferably 10 lb/in or more.

In another embodiment the adhesive compositions prepared herein have aPeel Strength on acrylic coated freezer paper at −18° C. of and aseparation speed of 5 cm per minute 0.05 lb/in or more, preferably 1lb/in or more, preferably 5 lb/in for more, preferably 10 lb/in or more.

In another embodiment, the adhesive prepared herein has deflection(measured in millimeters) of at least 100% greater than the sameadhesive without the functional component (preferably 150% greater, morepreferably 200% greater, more preferably 250% greater, more preferably300% greater, more preferably 350% greater, more preferably 400%greater, more preferably 500% greater, more preferably 600% greater) asmeasured by the following Three Point Bend procedure:

The adhesive “structure” is placed on top of 2 parallel, cylindricalbars of diameter 5 mm, separated by 33 mm. The long axis of the“structure” is perpendicular to the direction of the bars. Thetemperature is equilibrated at “T”° C. A third bar is lowered down ontothe “structure” in the centre to deflect it downwards. The deflection ismeasured to the break point of the “structure” or recorded as themaximum deflection of the apparatus. Definitions: “structure” is definedas a rectangular construction of 50 mm long, 6 mm wide and between 400and 600 microns thick. “T” is chosen to best represent the operatingconditions of the adhesive. In this case temperatures of −10° C. and−18° C. are typical values. “structure” preparation:

It is desired to make the “structure” as closely as possible to themethod used to prepare the adhesive bond. In this case the adhesive wasapplied hot at a temperature of 180° C. onto release paper. A firmstructure, coated in release paper, applied to the top of the adhesivein order to sandwich it between the two release papers. It wasimmediately rolled with a 1 kg PSA roller to compress the bond. When thebond is cooled, the adhesive is removed from between the two releasepapers and carefully cut to the desired dimensions.

For purposes of this invention and the claims thereto, the followingtests are used, unless otherwise indicated.

-   Tensile strength, Tensile strength at break and elongation at break    are measured by ASTM D 1708. Elongation at break is also called    strain at break or percent elongation.-   Peel strength −ASTM D-1876 (also referred to as Peel adhesion at    180° peel angle, 180° peel strength, 180° peel adhesion, T-Peel    strength, T-Peel.) Dynamic Storage modulus also called storage    modulus is G′.-   Creep resistance ASTM D-2293-   Rolling Ball Tack PSTC 6-   Hot Shear Strength is determined by suspending a 1000 gram weight    from a 25 mm wide strip of MYLAR polyester film coated with the    polymer or adhesive formulation which is adhered to a stainless    steel plate with a contact area of 12.5 mm×25 mm. The sample is    placed in a ventilated oven at 40° C. time is recorded until stress    failure occurs.-   Probe tack (also called Polyken probe tack) ASTM D 2979-   Holding Power—PSTC 7, also called Shear adhesion or Shear strength?.-   Density—ASTM D792 at 25° C.-   Gardner color ASTM D 1544-68.-   SAFT is also called heat resistance.-   Tensile Strength Modulus at 100% elongation and Young's Modulus are    determined according to ASTM E-1876.-   Luminence is the reflectance “Y” in the CIE color coordinates as    determined by ASTM D 1925 divided by 100.-   Needle penetration is measured by ASTM D5.-   Sag is also referred to as creep.-   Bond strength is measured by ASTM D3983.-   Adhesion to road surface is measured by ASTM D4541.

The adhesives of this invention can be used in any adhesive application,including but not limited to, disposables, packaging, laminates,pressure sensitive adhesives, tapes, labels, wood binding, paperbinding, non-wovens, road marking, reflective coatings, and the like.

In a preferred embodiment the adhesives of this invention can be usedfor disposable diaper and napkin chassis construction, elasticattachment in disposable goods converting, packaging, labeling,bookbinding, woodworking, and other assembly applications. Particularlypreferred applications include: baby diaper leg elastic, diaper frontaltape, diaper standing leg cuff, diaper chassis construction, diaper corestabilization, diaper liquid transfer layer, diaper outer coverlamination, diaper elastic cuff lamination, feminine napkin corestabilization, feminine napkin adhesive strip, industrial filtrationbonding, industrial filter material lamination, filter mask lamination,surgical gown lamination, surgical drape lamination, and perishableproducts packaging.

The adhesive compositions described above may be applied to anysubstrate. Preferred substrates include wood, paper, cardboard, plastic,thermoplastic, rubber, metal, metal foil (such as aluminum foil and tinfoil), metallized surfaces, cloth, non-wovens (particularlypolypropylene spunbonded fibers or non-wovens), spunbonded fibers,cardboard, stone, plaster, glass (including silicon oxide (SiO_(x))coatings applied by evaporating silicon oxide onto a film surface),foam, rock, ceramics, films, polymer foams (such as polyurethane foam),substrates coated with inks, dyes, pigments, PVDC and the like orcombinations thereof.

Additional preferred substrates include polyethylene, polypropylene,polyacrylates, acrylics, polyethylene terephthalate, or any of thepolymers listed above as suitable for blends.

Any of the above substrates, and/or the adhesive composition of thisinvention, may be corona discharge treated, flame treated, electron beamirradiated, gamma irradiated, microwaved, or silanized before or afterthe substrate and the adhesive composition are combined.

In preferred embodiments, the blends of this invention are heat stable,by which is meant that the Gardner color of the composition (asdetermined by ASTM D-1544-68) that has been heat aged (e.g., maintained)at or 180° C. for 48 hours, does not change by more than 7 Gardner unitswhen compared to the Gardner color of the initial composition.Preferably, the Gardner color of the composition after heating above itsmelting point for 48 hours does not change by more than 6, morepreferably 5, still more preferably 4, still more preferably 3, stillmore preferably 2, still more preferably 1 Gardner color unit, ascompared to the initial composition prior to being heated.

It has been discovered that free acid groups present in the compositionmay result in reduced heat stability. Accordingly, in a preferredembodiment, the amount of free acid groups present in the blend is lessthan about 1000 ppm, more preferably less than about 500 ppm, still morepreferably less than about 100 ppm, based on the total weight of theblend. In yet another preferred embodiment, the composition isessentially free from phosphites, preferably the phosphites are presentat 100 ppm or less.

In another embodiment this invention is also useful at low temperatures.

In another embodiment, this invention relates to:

-   1. An adhesive comprising 1) functionalized component and 2) an    olefin polymer comprising 50 weight % or more of an alpha-olefin    having 3 to 30 carbon atoms, where the olefin polymer has a Dot    T-Peel of 1 N or more on Kraft paper, an Mw of 10,000 to 100,000, a    g′ measured at the Mz of 0.95 or less and a heat of fusion of 1 to    70 J/g; where the functionalized component is selected from the    group consisting of functionalized polymers, functionalized    oligomers and beta nucleating agents; and where the Gardner color of    the adhesive does not change by more than 7 Gardner units when the    adhesive has been heat aged at 180° C. for 48 hours as compared to    the Gardner color of the unaged composition.-   2. An adhesive comprising 1) functionalized component and 2) an    olefin polymer comprising 50 weight % or more of one or more    alpha-olefins having 3 to 30 carbon atoms, where the olefin polymer    has a Dot T-Peel of 1 N or more, an Mw of 10,000 to 60,000, a g′    measured at the Mz of 0.98 or less, and a heat of fusion of 1 to 50    J/g; where the functionalized component is selected from the group    consisting of functionalized polymers, functionalized oligomers and    beta nucleating agents; and where the Gardner color of the adhesive    does not change by more than 7 Gardner units when the adhesive has    been heat aged at 180° C. for 48 hours as compared to the Gardner    color of the unaged composition.-   3. An adhesive comprising 1) functionalized component and 2) an    olefin polymer comprising a homopolypropylene or a copolymer of    propylene and up to 5 mole % ethylene having:    -   a) an isotactic run length of 1 to 30,    -   b) a percent of r dyad of greater than 20%, and    -   c) a heat of fusion of 70 J/g or less;        where the functionalized component is selected from the group        consisting of functionalized polymers, functionalized oligomers        and beta nucleating agents; and where the Gardner color of the        adhesive does not change by more than 7 Gardner units when the        adhesive has been heat aged at 180° C. for 48 hours as compared        to the Gardner color of the unaged composition.-   4. The adhesive of paragraph 1, 2 or 3 wherein the olefin polymer    has a percent crystallinity of between 5 and 40% or less.-   5. The adhesive of any of the above paragraphs wherein the g′ is    0.90 or less.-   6. The adhesive of any of the above paragraphs wherein the g′ is    0.80 or less.-   7. The adhesive of any of the above paragraphs wherein the olefin    polymer has a viscosity at 190° C. of 90,000 mPa·s or less.-   8. The adhesive of any of the above paragraphs wherein the olefin    polymer has a viscosity at 160° C. of 8,000 mPa·s or less.-   9. The adhesive of any of the above paragraphs wherein the olefin    polymer has a heat of fusion greater than 10 J/g.-   10. The adhesive of any of the above paragraphs wherein the olefin    polymer has heat of fusion of from 20 to 70 J/g.-   11. The adhesive of any of the above paragraphs wherein the olefin    polymer has heat of fusion of from 30 to 60 J/g.-   12. The adhesive of any of the above paragraphs wherein the olefin    polymer has a percent crystallinity of 10-30%.-   13. The adhesive of any of the above paragraphs wherein the olefin    polymer has tensile strength at break of 0.75 MPa or more.-   14. The adhesive of any of the above paragraphs wherein the olefin    polymer has a SAFT of 100-130° C.-   15. The adhesive of any of the above paragraphs wherein the olefin    polymer has an Mz/Mn of 2 to 200.-   16. The adhesive of any of the above paragraphs wherein the olefin    polymer has a Shore A hardness of 20-90.-   17. The adhesive of any of the above paragraphs wherein the olefin    polymer has a Dot T-Peel of between 3 and 10,000 N.-   18. The adhesive of any of the above paragraphs wherein the olefin    polymer has a Dot T-Peel of between 10 and 2,000 N.-   19. The adhesive of any of the above paragraphs wherein the olefin    polymer has a tensile strength at break of 0.6 MPa or more.-   20. The adhesive of any of the above paragraphs wherein the olefin    polymer has a Tg of between 5 and −65° C.-   21. The adhesive of any of the above paragraphs wherein the olefin    polymer comprises at least 50 weight % propylene.-   22. The adhesive of any of the above paragraphs wherein the olefin    polymer comprises at least 50 weight % propylene and up to 50 weight    % of a comonomer selected from the group consisting of ethylene,    butene, hexene, octene, decene, dodecene, pentene, heptene, nonene,    4-methyl-pentene-1,3-methyl pentene-1, 3,5,5-trimethyl-hexene-1, and    5-ethyl-1-nonene.-   23. The adhesive of any of the above paragraphs wherein the olefin    polymer comprises at least 50 weight % propylene and 5 weight % or    less of ethylene.-   24. The adhesive of any of the above paragraphs wherein the olefin    polymer comprises up to 10 weight % of a diene selected from the    group consisting of: butadiene, pentadiene, hexadiene, heptadiene,    octadiene, nonadiene, decadiene, undecadiene, dodecadiene,    tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene,    heptadecadiene, octadecadiene, nonadecadiene, icosadiene,    heneicosadiene, docosadiene, tricosadiene, tetracosadiene,    pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,    nonacosadiene, triacontadiene, cyclopentadiene, vinylnorbornene,    norbornadiene, ethylidene norbornene, divinylbenzene, and    dicyclopentadiene.-   25. The adhesive of any of the above paragraphs wherein tackifier is    present at 1 to 60 weight %.-   26. The adhesive of any of the above paragraphs wherein tackifier is    present and is selected from the group consisting of aliphatic    hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins,    hydrogenated polycyclopentadiene resins, polycyclopentadiene resins,    gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall    oil rosins, tall oil rosin esters, polyterpenes, aromatic modified    polyterpenes, terpene phenolics, aromatic modified hydrogenated    polycyclopentadiene resins, hydrogenated aliphatic resin,    hydrogenated aliphatic aromatic resins, hydrogenated terpenes and    modified terpenes, hydrogenated rosin acids, hydrogenated rosin    esters, derivatives thereof, and combinations thereof.-   27. The adhesive of any of the above paragraphs wherein the adhesive    further comprises one or more waxes selected from the group    consisting of polar waxes, non-polar waxes, Fischer-Tropsch waxes,    oxidized Fischer-Tropsch waxes, hydroxystearamide waxes,    polypropylene waxes, polyethylene waxes, wax modifiers, and    combinations thereof-   28. The adhesive of any of the above paragraphs wherein the adhesive    further comprises one or more additives selected from the group    consisting of plasticizers, oils, stabilizers, antioxidants,    pigments, dyestuffs, polymeric additives, defoamers, preservatives,    thickeners, rheology modifiers, humectants, fillers and water.-   29. The adhesive of any of the above paragraphs wherein the adhesive    further comprises one or more aliphatic naphthenic oils, white oils,    combinations thereof, or derivatives thereof.-   30. The adhesive of any of the above paragraphs wherein the adhesive    further comprises one or more plasticizers selected from the group    consisting of mineral oils, polybutenes, phthalates, and    combinations thereof.-   31. The adhesive of any of the above paragraphs wherein the adhesive    further comprises one or more plasticizers selected from the group    consisting of di-iso-undecyl phthalate, di-iso-nonylphthalate,    dioctylphthalates, combinations thereof, or derivatives thereof.-   32. The adhesive of any of the above paragraphs wherein the olefin    polymer has a peak melting point between 80 and 140° C.-   33. The adhesive of any of the above paragraphs wherein the olefin    polymer has a Tg of 0° C. or less.-   34. The adhesive of any of the above paragraphs wherein the olefin    polymer has a melt index of 50 dg/min or more.-   35. The adhesive of any of the above paragraphs wherein the olefin    polymer has a set time of 30 seconds or less.-   36. The adhesive of any of the above paragraphs wherein the olefin    polymer has a Tc that is at least 10° C. below the Tm.-   37. The adhesive of any of the above paragraphs wherein the olefin    polymer has an I₁₀/I₂ of 6.5 or less.-   38. The adhesive of any of the above paragraphs wherein the olefin    polymer has a range of crystallization of 10 to 60° C. wide.-   39. The adhesive of any of the above paragraphs wherein the    functionalized component is present at 0.001 to 50 weight %.-   40. The adhesive of any of the above paragraphs wherein the    functionalized component is present at 0.1 to 10 weight %.-   41. The adhesive of any of the above paragraphs wherein the    functionalized component comprises functionalized polymer.-   42. The adhesive of any of the above paragraphs wherein the    functionalized component comprises functionalized polymer selected    from the group consisting of maleated polyethylene, maleated    metallocene polyethylene, maleated metallocene polypropylene,    maleated ethylene propylene rubber, and functionalized    polyisobutylene.-   43. The adhesive of any of the above paragraphs wherein the    functionalized component comprises functionalized oligomer.-   44. The adhesive of any of the above paragraphs wherein the    functionalized component comprises functionalized hydrocarbon resin.-   45. The adhesive of any of the above paragraphs wherein the    functionalized component comprises a beta-nucleating agent.-   46. The adhesive of any of the above paragraphs wherein the    functionalized component comprises beta nucleating agent selected    from the group consisting of N,N′-diphenylhexanediamide,    N,N′-dicyclohexylterephthalamide,    N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide,    N,N′-dicyclohexanecabonyl-p-phenylenediamine,    N,N′-dibenzoyl-1,5-diaminonaphthalene,    N,N′-dibenzoyl-1,4-diaminocyclohexane or    N,N′-dicyclohexanecarbonyl-1,4-diaminocyclohexane,    N-cyclohexyl-4-(N-cyclohexylcarbonylamino)benzamide,    N-phenyl-5-(N-benzoylamino)pentanamide, sorbitol, salicyclic acid,    p-hydroxybenzoic acid, zinc 3,5-di-tert-butylsalicyclate,    2-naphthoic acid, phenyl acetic acid, terephthalic acid, anthranilic    acid, 3,3-diphenylpropionic, tetra butyl ammonium chloride,    naphthalic acid, benzoin, ascorbic acid, adipic acid, tertabutyl    benzoate, dodecylbenzenesulfonic acid sodium salt,    4-dodecylbenzenesulfonic acid, 4,4-bis(4-hydroxyphenyl)valeric acid,    diphenic acid, 4-isopropylbenzoic acid, Millad 3988tm, neodecanoic    acid, abietic acid, sodium benzoate, succinic anhydride, phenol,    benzoic acid, benzyl alcohol, benzyl amine, alkyl substituted    succinates (preferably C1 to C40 alkyl substituted succinates),    substituted di(benzylidene)-D-sorbitols,    1,3:2,4-di(benzylidene)-D-sorbitol,    1,3:2,4-bis(3,4-dimethylbenzylidene)-D-sorbitol, red quinacridone    dye, gamma-crystalline form of a quinacridone colorant, the bisodium    salt of orthophthalic acid, the aluminum salt of 6-quinizarin    sulfonic acid, the aluminum salt of isophthalic and the aluminum    salt of terephthalic acids.-   47. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional group selected from the    group consisting of organic acids, organic amides, organic amines,    organic esters, organic anhydrides, organic alcohols, organic acid    halides, organic peroxides, and salts thereof.-   48. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional group selected from the    group consisting of carboxylic acids, esters of the unsaturated    carboxylic acids, acid anhydrides, di-esters, salts, amides, imides,    aromatic vinyl compounds hydrolyzable unsaturated silane compounds    and unsaturated halogenated hydrocarbons.-   49. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional group selected from the    group consisting of maleic anhydride, citraconic anhydride, 2-methyl    maleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleic    anhydride, bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic anhydride and    4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid,    methacrylic acid, maleic acid, fumaric acid, itaconic acid,    citraconic acid, mesaconic acid, crotonic acid,    bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride,    1,2,3,4,5,&g, lo-octahydronaphthalene-2,3-dicarboxylic acid    anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene,    bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride,    maleopimaric acid, tetrahydrophtalic anhydride,    norborn-5-ene-2,3-dicarboxylic acid anhydride, nadic anhydride,    methyl nadic anhydride, himic anhydride, methyl himic anhydride, and    x-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride    (XMNA).-   50. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is syndiotactic polypropylene.-   51. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is syndiotactic rich    polypropylene.-   52. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is polypropylene having a weight    average molecular weight of 15,000 or less and a crystallinity of 5%    or more.-   53. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is polypropylene having a weight    average molecular weight between 3,000 to 15,000 and a crystallinity    of 5% or more functionalized with up to 10 weight % of maleic    anhydride.-   54. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is polypropylene having:    -   1) a heat of fusion from about 0.5 J/g to about 25 J/g; and/or    -   2) a crystallinity of about 0.25% to about 15%; and/or    -   3) a melting point of from about 25° C. to about 75° C.; and/or    -   4) a weight average molecular weight, prior to        functionalization, of 10,000 to 500,000; and/or    -   5) an M_(w)/M_(i), between 1.8 to 5; and/or    -   6) a Mooney viscosity ML (1+4)@125° C. less than 100.-   55. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is syndiotactic rich polypropylene    having at least 50% [r] dyads.-   56. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is syndiotactic rich polypropylene    having at less than or equal to 99% [r] dyads.-   57. The adhesive of any of the above paragraphs wherein the    functional component comprises a functional polymer where the    polymer of the functional polymer is a random copolymer of propylene    and an alpha olefin wherein the propylene copolymer has:    -   a crystallinity of from 0.1 to 50%;-   a propylene content from 68 to 92 mole percent;-   a comonomer content from 8 to 32 mole percent;-   a melting point from 25° C. to 105° C.; and-   a heat of fusion of less than 45 J/g.-   58. A process to make the adhesive of any of the above paragraphs,    comprising the steps of contacting the olefin polymer with the    functionalized component to produce an admixture.-   59. A tie layer, paint primer, package, article, disposable article,    diaper, film, laminate, pressure sensitive adhesive, hot melt    adhesive, tape or nonwoven fabric comprising the adhesive of any of    the above claims.-   60. The adhesive of any of the above paragraphs wherein the adhesive    shows substrate fiber tear at −10° C. when the adhesive is applied    to 50 pound corrugated cardboard.-   61. The adhesive of any of the above paragraphs wherein the adhesive    shows substrate fiber tear at −10° C. of at least 5% when the    adhesive is applied to 50 pound corrugated cardboard.-   62. The adhesive of any of the above paragraphs wherein the adhesive    has three point bend deflection at −10° C. of at least 100% greater    than the same adhesive without the functional component.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby.

EXAMPLES

Characterization and Tests

Molecular weights (number average molecular weight (Mn), weight averagemolecular weight (Mw), and z-average molecular weight (Mz)) weredetermined using a Waters 150 Size Exclusion Chromatograph (SEC)equipped with a differential refractive index detector (DRI), an onlinelow angle light scattering (LALLS) detector and a viscometer (VIS). Thedetails of the detector calibrations have been described elsewhere[Reference: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley,Macromolecules, Volume 34, Number 19, 6812-6820, (2001)]; attached beloware brief descriptions of the components.

The SEC with three Polymer Laboratories PLgel 10 mm Mixed-B columns, anominal flow rate 0.5 cm³/min, and a nominal injection volume 300microliters was common to both detector configurations. The varioustransfer lines, columns and differential refractometer (the DRIdetector, used mainly to determine eluting solution concentrations) werecontained in an oven maintained at 135° C.

The LALLS detector was the model 2040 dual-angle light scatteringphotometer (Precision Detector Inc.). Its flow cell, located in the SECoven, uses a 690 nm diode laser light source and collects scatteredlight at two angles, 15° and 90°. Only the 15° output was used in theseexperiments. Its signal was sent to a data acquisition board (NationalInstruments) that accumulates readings at a rate of 16 per second. Thelowest four readings were averaged, and then a proportional signal wassent to the SEC-LALLS-VIS computer. The LALLS detector was placed afterthe SEC columns, but before the viscometer.

The viscometer was a high temperature Model 150R (Viscotek Corporation).It consists of four capillaries arranged in a Wheatstone bridgeconfiguration with two pressure transducers. One transducer measures thetotal pressure drop across the detector, and the other, positionedbetween the two sides of the bridge, measures a differential pressure.The specific viscosity for the solution flowing through the viscometerwas calculated from their outputs. The viscometer was inside the SECoven, positioned after the LALLS detector but before the DRI detector.

Solvent for the SEC experiment was prepared by adding 6 grams ofbutylated hydroxy toluene (BHT) as an antioxidant to a 4 liter bottle of1,2,4 Trichlorobenzene (TCB) (Aldrich Reagent grade) and waiting for theBHT to solubilize. The TCB mixture was then filtered through a 0.7micron glass pre-filter and subsequently through a 0.1 micron Teflonfilter. There was an additional online 0.7 micron glass pre-filter/0.22micron Teflon filter assembly between the high pressure pump and SECcolumns. The TCB was then degassed with an online degasser (Phenomenex,Model DG-4000) before entering the SEC.

Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units were 1.463 g/ml at room temperatureand 1.324 g/ml at 135° C. The injection concentration ranged from 1.0 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples.

Prior to running each sample the DRI detector and the injector werepurged. Flow rate in the apparatus was then increased to 0.5 ml/minute,and the DRI was allowed to stabilize for 8-9 hours before injecting thefirst sample. The argon ion laser was turned on 1 to 1.5 hours beforerunning samples by running the laser in idle mode for 20-30 minutes andthen switching to full power in light regulation mode.

The branching index was measured using SEC with an on-line viscometer(SEC-VIS) and are reported as g′ at each molecular weight in the SECtrace. The branching index g′ is defined as:

$g^{\prime} = \frac{\eta_{b}}{\eta_{l}}$where η_(b) is the intrinsic viscosity of the branched polymer and η₁ isthe intrinsic viscosity of a linear polymer of the sameviscosity-averaged molecular weight (M_(v)) as the branched polymer.η₁=KM_(v) ^(α), K and α were measured values for linear polymers andshould be obtained on the same SEC-DRI-LS-VIS instrument as the one usedfor branching index measurement. For polypropylene samples presented inthis invention, K=0.0002288 and α=0.705 were used. The SEC-DRI-LS-VISmethod obviates the need to correct for polydispersities, since theintrinsic viscosity and the molecular weight were measured at individualelution volumes, which arguably contain narrowly dispersed polymer.Linear polymers selected as standards for comparison should be of thesame viscosity average molecular weight, monomer content and compositiondistribution. Linear character for polymer containing C2 to C10 monomersis confirmed by Carbon-13 NMR the method of Randall (Rev. Macromol.Chem. Phys., C29 (2&3), p. 285-297). Linear character for C11 and abovemonomers is confirmed by GPC analysis using a MALLS detector. Forexample, for a copolymer of propylene, the NMR should not indicatebranching greater than that of the co-monomer (i.e. if the comonmer isbutene, branches of greater than two carbons should not be present). Fora homopolymer of propylene, the GPC should not show branches of morethan one carbon atom. When a linear standard is desired for a polymerwhere the comomoner is C9 or more, one can refer to T. Sun, P. Brant, R.R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001) for protocols on determining standards for thosepolymers. In the case of syndiotactic polymers, the standard should havea comparable amount of syndiotacticty as measured by Carbon 13 NMR.

Peak melting point (Tm), peak crystallization temperature (Tc), heat offusion and crystallinity were determined using the following procedureaccording to ASTM E 794-85. Differential scanning calorimetric (DSC)data was obtained using a TA Instruments model 2920 machine. Samplesweighing approximately 7-10 mg were sealed in aluminum sample pans. TheDSC data was recorded by first cooling the sample to −50° C. and thengradually heating it to 200° C. at a rate of 10° C./minute. The samplewas kept at 200° C. for 5 minutes before a second cooling-heating cyclewas applied. Both the first and second cycle thermal events wererecorded. Areas under the curves were measured and used to determine theheat of fusion and the degree of crystallinity. The percentcrystallinity is calculated using the formula, [area under the curve(Joules/gram)/B (Joules/gram)]*100, where B is the heat of fusion forthe homopolymer of the major monomer component. These values for B areto be obtained from the Polymer Handbook, Fourth Edition, published byJohn Wiley and Sons, New York 1999. A value of 189 J/g (B) was used asthe heat of fusion for 100% crystalline polypropylene. For polymersdisplaying multiple melting or crystallization peaks, the highestmelting peak was taken as peak melting point, and the highestcrystallization peak was taken as peak crystallization temperature.

The glass transition temperature (Tg) was measured by ASTM E 1356 usinga TA Instruments model 2920 machine.

Melt Viscosity (ASTM D-3236) (also called “viscosity”, “Brookfieldviscosity”)

Melt viscosity profiles were typically measured at temperatures from120° C. to 190° C. using a Brookfield Thermosel viscometer and a number27 spindle.

Adhesive Testing

A number of hot melt adhesives were prepared by using the pure polymersor blending the pure polymer, functionalized additives, tackifier, wax,antioxidant, and other ingredients under low shear mixing at elevatedtemperatures to form fluid melt. The mixing temperature varied fromabout 130 to about 190° C. Adhesive test specimens were created bybonding the substrates together with a dot of about 0.3 grams of moltenadhesive and compressing the bond with a 500-gram weight until cooled toroom temperature. The dot size was controlled by the adhesive volumesuch that in most cases the compressed disk which formed gave a uniformcircle just inside the dimensions of the substrates.

Once a construct has been produced it can be subjected to variousinsults in order to assess the effectiveness of the bond. Once a bondfails to a paper substrate a simple way to quantify the effectiveness isto estimate the area of the adhesive dot that retained paper fibers asthe construct failed along the bond line. This estimate was calledpercent substrate fiber tear. An example of good fiber, afterconditioning a sample for 15 hours at −12° C. and attempting to destroythe bond, would be an estimate of 80-100% substrate fiber tear. It islikely that 0% substrate fiber tear under those conditions would signala loss of adhesion.

Substrate fiber tear: The specimens were prepared using the sameprocedure as that described above. For low temperature fiber tear test,the bond specimens were placed in a freezer or refrigerator to obtainthe desired test temperature. For substrate fiber tear at roomtemperature, the specimens were aged at ambient conditions. The bondswere separated by hand and a determination made as to the type offailure observed. The amount of substrate fiber tear was expressed inpercentage.

Dot T-Peel was determined according to ASTM D 1876, except that thespecimen was produced by combining two 1 inch by 3 inch (2.54 cm×7.62cm) substrate cut outs with a dot of adhesive with a volume that, whencompressed under a 500-gram weight occupied about 1 square inch of area(1 inch=2.54 cm). Once made all the specimens were pulled apart in sideby side testing at a rate of 2 inches per minute by a machine thatrecords the destructive force of the insult being applied. The maximumforce achieved for each sample tested was recorded and averaged, thusproducing the average maximum force which is reported as the Dot T-Peel.

Peel Strength (modified ASTM D1876): Substrates (1×3 inches (25×76 mm))were heat sealed with adhesive film (5 mils (130 μm) thickness) at 135°C. for 1 to 2 seconds and 40 psi (0.28 MPa) pressure. Bond specimenswere peeled back in a tensile tester at a constant crosshead speed of 2in/min (51 mm/min). The average force required to peel the bond (5specimens) apart is recorded.

Set time is defined as the time it takes for a compressed adhesivesubstrate construct to fasten together enough to give substrate fibertear when pulled apart, and thus the bond is sufficiently strong toremove the compression. The bond will likely still strengthen uponfurther cooling, however, it no longer requires compression. These settimes were measured by placing a molten dot of adhesive on to a filefolder substrate taped to a flat table. A file folder tab (1 inch by 3inch (2.5 cm×7.6 cm)) was placed upon the dot 3 seconds later andcompressed with a 500 gram weight. The weight was allowed to sit forabout 0.5 to about 10 seconds. The construct thus formed was pulledapart to check for a bonding level good enough to produce substratefiber tear. The set time was recorded as the minimum time required forthis good bonding to occur. Standards were used to calibrate theprocess.

SAFT (modified D4498) measures the ability of a bond to withstand anelevated temperature rising at 10° F. (5.5° C.)/15 min., under aconstant force that pulls the bond in the shear mode. Bonds were formedin the manner described above on Kraft paper (1 inch by 3 inch (2.5cm×7.6 cm)). The test specimens were suspended vertically in an oven atroom temperature with a 500-gram load attached to the bottom. Thetemperatures at which the weight fell was recorded (when the occasionalsample reached temperatures above the oven capacity >265° F. (129° C.)it was terminated and averaged in with the other samples at terminationtemperature).

Shore A hardness was measured according to ASTM D 2240. An air cooleddot of adhesive was subjected to the needle and the deflection wasrecorded from the scale.

The following materials were used in examples HM1 through HM50 listed inthe following tables.

Trade name Description Source Tackifiers Escorez ® 5637 Hydrogenatedaromatic modified resin ExxonMobil produced from dicyclopentadieneChemical Company feedstock, exhibiting a ring and ball softening pointof 130° C. Escorez ® 5690 hydrogenated aromatic modified resinExxonMobil produced from dicyclopentadiene Chemical Company feedstock,exhibiting a ring and ball softening point of 90° C. Oils Kadol oilRefined white mineral oil Witco Polymers/Adhesives Rextac RT 2715 C3/C4Ziegler Natta APAO Huntsman, Odessa Texas Henkel hot melt 80- Commercialblend of EVA, tackifier, and Henkel Corp 8368 wax Advantra 9250Commercial blend of C2/C8 metallocene H. B. Fuller polymers, tackifiers,and wax Tite bond wood Water based adhesive Home Depot, glue Houston,Texas VM-1000 is a propylene ethylene copolymer (approx. ExxonMobil   wt % C2) produced using a metallocene Chemical Company catalyst sold asVM-1000 VM-2000 is a propylene ethylene copolymer (approx. ExxonMobil 14wt % C2) produced using a metallocene Chemical Company catalyst sold asVM-2000 VM-3000 is a propylene ethylene copolymer (approx. ExxonMobil 11wt % C2) produced using a metallocene Chemical Company catalyst sold asVM-3000 Waxes/Funtionalized additives AC395A Oxidized polyethylene withdensity of 1.0 g/cc, Honeywell, viscosity of 2500 cP at 150° C. andMorristown, New acid number of 45~50 mg/KOH/g. Jersey AC 596PPolypropylene-maleic anhydride Honeywell, copolymer with viscosity 189cps at 190° C. Morristown, New and Saponification number of 40 mg/KOH/gJersey AC 597 Polypropylene-maleic anhydride Honeywell, copolymer withviscosity 374 cps at 190° C. Morristown, New and Saponification numberof 80 mg/KOH/g Jersey AC X1325 Polypropylene-maleic anhydride Honeywell,copolymer with viscosity 1490 cps at 190° C. Morristown, New and acidnumber of 16 mg/KOH/g Jersey AC1302P Ethylene-maleic anhydride copolymerwith Honeywell, viscosity of 248 cP at 190° C. and Morristown, NewSaponification number of 5 mg KOH/g Jersey PP-grafted maleic PP-graftedmaleic anhydride with averaged Sigma-Aldrich, anhydride M_(w) of ~9,100,M_(n) of ~3,900 by GPC, Product number: viscosity of 400 cP at 190° C.,acid number 42784-5 of 47 mg KOH/g, softening point of 157° C. (ring andball) and density of 0.934 g/mL. MAPP 40 Maleated polypropylene withacid value of Chusei, Pasadena 45~50, viscosity at 190° C. of 400-425cP, Texas and softening point of 143~155° C. Paraflint H-1Fisher-Tropsch wax, 10 mPa @ 250° F. Moore and Munger C80 wax FischerTropsch fractionated Moore and Munger polypropylene wax Antioxidants andother additives Irganox 1010 Phenolic antioxidant Ciba-Geigy Testsurfaces (substrates) Paperboard 84B generic poster board clay coatednewsprint Huckster Packaging and Supply, Houston, TX Paperboard 84Cgeneric corrugated cardboard 200# stock Huckster Packaging and Supply,Houston, TX Inland paper board High Performance box board Inland PaperBoard and Packaging Company of Rome Black white fabric Printed stretch100% Cotton with a Thread High Fashion Count of 17 by 13 per square cm,a more Fabrics, Houston loosely woven fabric Texas Formica tabs weremade from standard sheet Lowe's Hardware, Formica Houston Texas Bluefabric tabs were made from Blue Stock 038C0TP High Fashion 100% Cotton,Thread Count 21by 45 per Fabrics, Houston square cm with a weight of0.022 grams Texas. per square cm, a tightly woven cotton fabric Setoncatalog paper book paper bound by a hot melt process as Seton Catalogdetermined from examination PET Polyester (PET), Commonly called MylarSeveral Sources Kraft paper Kraft paper Georgia Pacific, Atlanta,Georgia File folder File folder is a typical manila letter size SmeadPaper, stock (⅓ cut) stock having a minimum of 10% number 153L, UPC postconsumer recycle paper content number 10330 PP cast film An orientedpolypropylene cast film made ExxonMobil from ESCORENE PP 4772. ChemicalCompany

Polymers used for adhesive evaluation in the following examples wereproduced according to the following procedure. Polymerization wasperformed in a liquid filled, single-stage continuous reactor usingmixed metallocene catalyst systems. The reactor was a 0.5-literstainless steel autoclave reactor and was equipped with a stirrer, awater-cooling/steam-heating element with a temperature controller, and apressure controller. Solvents, monomers such as ethylene and propylene,and comonomers (such as butene and hexene), if present, were firstpurified by passing through a three-column purification system. Thepurification system consisted of an Oxiclear column (Model #RGP-R1-500from Labelear) followed by a 5A and a 3A molecular sieve columns.Purification columns were regenerated periodically whenever there isevidence of lower activity of polymerization. Both the 3A and 5Amolecular sieve columns were regenerated in-house under nitrogen at aset temperature of 260° C. and 315° C., respectively. The molecularsieve material was purchased from Aldrich. Oxiclear column wasregenerated in the original manufacture.

The solvent, monomers and comonomers were fed into a manifold first.Ethylene from in-house supply was delivered as a gas solubilized in thechilled solvent/monomer mixture in the manifold. The mixture of solventand monomers were then chilled to about −15° C. by passing through achiller before fed into the reactor through a single tube. All liquidflow rates were measured using Brooksfield mass flow meters orMicro-Motion Coriolis-type flow meters. Ethylene flow rate was meteredthrough a Brookfield mass flow controller

The catalyst compounds used to produce semi-crystalline polypropylenewere rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl(obtained from Albemarle) andrac-1,2-ethylene-bis(4,7-dimethylindenyl)hafnium dimethyl (obtained fromBoulder Scientific Company).

The catalyst compounds used to produce amorphous polypropylene were,dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl (Obtained from Albemarle) and[di(p-triethylsilylphenyl)methylene](cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafnium dimethyl (Obtained from Albemarle).

The catalysts were preactivated with N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate (obtained from Albemarle) at a molarratio of 1:1 to 1:1.1 in 700 ml of toluene at least 10 minutes prior tothe polymerization reaction. The catalyst systems were diluted to aconcentration of catalyst ranging from 0.2 to 1.4 mg/ml in toluene. Allcatalyst solutions were kept in an inert atmosphere with <1.5 ppm watercontent and fed into reactor by metering pumps. The catalyst solutionwas used for all polymerization runs carried out in the same day. Newbatch of catalyst solution was prepared in case that more than 700 ml ofcatalyst solution was consumed in one day.

In cases of polymerization involving multiple catalyst, each catalystsolution was pumped through separate lines, and then mixed in amanifold, and fed into the reactor through a single line. The connectingtube between the catalyst manifold and reactor inlet was about 1 meterlong. The contact of catalyst, solvent and monomers took place in thereactor. Catalyst pumps were calibrated periodically using toluene asthe calibrating medium. Catalyst concentration in the feed wascontrolled through changing the catalyst concentration in catalystsolution and/or changing in the feed rate of catalyst solution. The feedrate of catalyst solution varied in a range of 0.2 to 5 ml/minute.

As an impurity scavenger, 55 ml of tri-iso-butyl aluminum (25 wt. % intoluene, Akzo Noble) was diluted in 22.83 kilogram of hexane. Thediluted tri-iso-butyl aluminum solution was stored in a 37.9-litercylinder under nitrogen blanket. The solution was used for allpolymerization runs until about 90% of consumption, and then a new batchwas prepared. Feed rates of the tri-iso-butyl aluminum solution variedfrom polymerization reaction to reaction, ranging from 0 (no scavenger)to 4 ml per minutes.

For polymerization reactions involving alpha, omega-dienes,1,9-decadiene was diluted to a concentration ranging from 4.8 to 9.5vol. % in toluene. The diluted solution was then fed into reactor by ametering pump through a comonomer line. The 1,9-decadiene was obtainedfrom Aldrich and was purified by first passing through alumina activatedat high temperature under nitrogen, followed by molecular sieveactivated at high temperature under nitrogen.

The reactor was first cleaned by continuously pumping solvent (e.g.,hexane) and scavenger through the reactor system for at least one hourat a maximum allowed temperature (about 150° C.). After cleaning, thereactor was heated/cooled to the desired temperature using water/steammixture flowing through the reactor jacket and controlled at a setpressure with controlled solvent flow. Monomers and catalyst solutionswere then fed into the reactor when a steady state of operation wasreached. An automatic temperature control system was used to control andmaintain the reactor at a set temperature. Onset of polymerizationactivity was determined by observations of a viscous product and lowertemperature of water-steam mixture. Once the activity was establishedand system reached steady state, the reactor was lined out by continuingoperating the system under the established condition for a time periodof at least five times of mean residence time prior to samplecollection. The resulting mixture, containing mostly solvent, polymerand unreacted monomers, was collected in a collection box after thesystem reached a steady state operation. The collected samples werefirst air-dried in a hood to evaporate most of the solvent, and thendried in a vacuum oven at a temperature of about 90° C. for about 12hours. The vacuum oven dried samples were weighed to obtain yields. Allthe reactions were carried out at a pressure of 2.41 MPa-gauge and inthe temperature range of 110 to 130° C.

The detailed experimental conditions and analytical results for polymersamples PP1 through PP9 are presented in Tables 1.

TABLE 1 Detailed polymerization reaction conditions Polymer PP1 PP2 PP3PP4 PP5 PP6 PP7 PP8 PP9 Catalyst #1 A A A B B B B B B Catalyst #12.09E−06 5.22E−06 6.53E−06 1.32E−06 1.32E−06 2.35E−06 1.77E−06 1.32E−068.83E−07 feed rate (mole/min) Catalyst #2 C D D D D D D D D Catalyst #24.25E−07 7.65E−07 4.74E−07 1.42E−07 1.42E−07 1.44E−07 1.44E−07 1.44E−071.44E−07 feed rate (mole/min) Propylene feed 14 14 14 14 14 14 14 14 14rate (g/min) 1,9 decadiene — 2.24 0.19 — — — — — — feed rate (ml/min)Hexane feed 90 90 90 90 90 90 90 90 90 rate (ml/min) Polymerization 110117 115 130 125 127 126 124 122 temperature (° C.) Mn (kg/mol) 12.2 —17.3 11.3 13 — — — — Mw (kg/mol) 30.6 — 34.5 25.2 31.3 — — — — Mz(kg/mol) 84.3 — 97.1 47.9 59.8 — — — — g′ @ Mz — — 0.75 0.92 0.88 — — —— Tc (° C.) 72.3 87.0 88.5 94.1 94.5 75.7 84.5 89.8 93.4 Tm (° C.) 112.1133.7 136.3 131.8 131.5 117.6 123.3 127.2 130.8 Tg (° C.) −22.4 −10.7−12.4 −6.4 −9.3 −7.9 −7.6 −6.4 −6.9 Heat of fusion 23.3 39.5 35.8 48.447.3 24.2 34.1 41.9 51.9 (J/g) Viscosity 1420 518 1040 877 1310 1010 9201140 1077 @190° C. (cp) Catalysts: A:dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titaniumdimethyl B:di(p-triethylsilylphenyl)methylene](cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl C: rac-1,2-ethylene-bis(4,7-dimethylindenyl)hafnium dimethyl D:rac-dimethylsilyl bis(2-methyl-4-phenylindenyl) zirconium dimethyl

The detailed experimental conditions and analytical results for polymersamples SP1, SP3 through SP6 are presented below. The catalyst used wasdiphenylmethylene(cyclopentaidenyl)(fluorenyl)hafnium dimethyl and theactivator was N,N-dimethylaniliniumtertakis(pentafluorophenyl)borate.

Detailed reaction condition and analytical data Polymer SP5 SP4 SP3 SP6SP1 Polymerization temperature (° C.) 94 107 120 90 110 Catalyst feedrate (mol/min) 1.75E−06 1.75E−06 1.75E−06 8.76E−07 1.75E−06 Propylene(g/min) 14 14 14 14 14 Hexane feed rate (ml/min) 90 90 90 90 90 Mn(kg/mol) 97.114 42.291 22.663 171.496 23 Mw (kg/mol) 177.094 87.19645.041 279.851 62 Mz (kg/mol) 287.865 146.844 79.39 423.637 148 Triadmole fraction from C13 NMR mm 0.1135 0.1333 0.1522 0.0922 mr + rm 0.43520.4639 0.4831 0.3992 rr 0.4513 0.4028 0.3646 0.5085 Diad mole fractionfrom C13 NMR m 0.3311 0.3653 0.3938 0.2918 r 0.6689 0.6347 0.6062 0.7082

Polymer samples PP10, PP11 and PP12 were produced in two continuousstirred tank reactors in series. The reactors were operated liquid fullunder a pressure of 3.65 MPa. The temperatures of both reactors werecontrolled through hot oil circulation in the reactor jacket. Theresidence time of the feed in each reactor was 45 minutes. Conversion ofpropylene to polymer product was about 91%. Propylene feed at the rateof 3.63 kg/hour was combined with hexane at 7.71 kg/hour to form 11.34kg/hour of reactor feed solution. Tri-n-octyl aluminum (TNOA) as a 3 wt.% solution in hexane (obtained from Albemarle) was introduced into thisstream at the rate of 0.272 gram/hour (active basis). Catalyst andactivator entered the reactor from a separate port. The catalystsolution consisted of a mixture ofdi(p-triethylsilylphenyl)methylene](cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl (catalyst B) and rac-dimethylsilylbis(2-methyl-4-phenylindenyl) zirconium dimethyl (catalyst D). Thecatalyst solution was prepared by dissolving the catalyst mixture intoluene to form a 0.5 wt-% solution. The activator feed stream was madeup of a 0.2 wt-% solution of N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate in toluene. Both the catalysts andactivator were obtained from Albemarle. The catalyst and activator feedlines were configured to mix in line immediately upstream of the firstreactor, with an estimated contact time of 2˜4 minutes. The catalyst andactivator feed rates were 0.04 gram/hour and 0.1 gram/hour (activebasis) respectively. Molten polymer was recovered from solution via twoflash stages, each with a preheater. The first stage (20 psig) polymercontained about 2% solvent and the second stage (50 torr vacuum)incorporated about 800 ppm volatile. Water was injected into the secondstage flash (devolatilizer) feed to quench residual catalyst and aidwith solvent stripping. The properties of the polymer and the reactionconditions are summarized in the table below.

Detailed polymerization condition for samples PP10 to PP12 Polymer PP10PP11 PP12 Catalyst B in catalyst mixture (mol. %) 93 86 86Polymerization temperature in leading 134 130 131 reactor (° C.)Polymerization temperature in trailing — 131 131 reactor (° C.)Scavenger concentration in feed (wppm) 24 24.5 24.5 Catalystconcentration in feed (wppm) 4.1 4.1 4.1 Activator concentration in feed(wppm) 73.5 73.5 73.5 Propylene concentration in feed (wt. %) 28 28.628.6 Conversion (%) 91 — quench water (gram/hour) — 2.72 2.72 Viscosity@ 190° C. (cP) 1105 1600 1522 Shore A hardness 80 — Mw (kg/mol) 32.541.1 40.6 Mn (kg/mol) 13.2 19.6 20.7 Mz (kg/mol) 62.8 76 72.5 g′ @ Mz0.85 0.82 Tc (° C.) 74.8 77.8 68.6 Tm (° C.) 133 132 132 Heat of fusion(J/g) 30.6 28.7 29.5

The following polymers were maleated and used as a modifier for adhesionenhancement. The functionalization was carried out by dissolving 120 gof polymer in toluene (polymer concentration is about 20 wt. %) and thencombining with 15 wt. % (based on polymer) of maleic anhydride (“MA”)and 2.5 wet % of 2,5-dimethyl-2,5-di(t-butylperoxyl)hexene. The reactiontemperature was maintained at 139° C. for 4 hours. The method describedby M. Sclavons et al. (Polymer, 41 (2000), page 1989) was used todetermine the MA content of the maleated polymers. Briefly, about 0.5gram of polymer was dissolved in 150 ml of toluene at the boilingtemperature. A potentiometric titration with tetra-butylammoniumhydroxide using bromothymol blue as the color indicator was performed onthe heated solution in which the polymer did not precipitate during thetitration. The molecular weight and MA content of the maleated polymersare listed below.

Modifier # SP6-g-MA SP4-g-MA SP3-g-MA PP12-g-MA Polymer SP6 SP4 SP3 PP12Mn (kg/mol) 60 23 17 12 Mw (kg/mol) 135 44 33 36.5 Mz (kg/mol) 263 71 5564.7 MA. (wt. %) 1.12 1 1.92 1.41

The following polymers were maleated and used as a modifier for adhesionenhancement. The maleation was carried out by following the proceduredescribed in WO 02/36651.

TABLE 5 Modifier # VM-3000-g-MA VM-2000-g-MA EP3-g-MA Polymer VM-3000VM-2000 EP-3 Mn (kg/mol) 17 16 36 Mw (kg/mol) 74 66 63 Mz (kg/mol) 116103 89 MA (wt. %) 1.92 1.98 Ethylene 10.7 14.4 10 content (wt. %)

A number of hot melt adhesives were prepared by using the polymers orblending the polymer, functionalized additives, tackifier, wax,antioxidant, and other ingredients under low shear mixing at elevatedtemperatures to form fluid melt. The mixing temperature varies fromabout 130 to about 190° C. As examples, The tables below list thedetailed formulation and the properties of blends. All the adhesiontests were conducted at ambient condition unless otherwise noted. Theformulations are in weight percent.

Adhesion tests on various substrates Formulation HM1 HM2 HM3 HM4 HM5 HM6Polymer/adhesive REXTAC REXTAC PP10 PP10 PP10 Tite Bond 2715 2715 WoodGlue Polymer (wt. %) 100  91  100  91 91 100 Paraflint H-1 (wt. %) 0 0 00 3 0 Escorez 5637 (wt. %) 0 3 0 3 3 0 MAPP 40 (wt. %) 0 0 0 0 3 0 AC1302P (wt. %) 0 6 0 6 0 0 Shore “A” hardness 26  22  53  56 53 — Settime (sec)  6+  6+  6+ 2.5 3 — Viscosity @ 190° C. 1730   1422   1340  1090 1020 — (cps) Adhesion (Dot T-peel) and failure types Mylar (PET)aged 4 cf, 3.896 cf, 5.366 ss, af, ss, af, ss, cf, af, cf, days 1.0871.488 4.629 0.1517 Seton catalog paper sf, 1.113 sf, 1.337 sf, 1.091 sf,1.131 sf, 0.8797 sf, 0.944 aged 4 days Blue fabric to cf, 5.457 cf,5.608 cf, 5.401 cf, 5.974 cf, 8.232 cf, 20.79 Formica aged 4 days Blackwhite fabric to cf, 3.001 cf, 4.210 cf, 3.681 cf, 4.066 cf, 5.874 ss,cf, Formica aged 4 days 18.92 PP cast film 4.643 cf cf, 6.56 cf, af, ab,cf, af, cf, af, would not laminate aged 4 days 7.233 3.587 3.140 dryKraft paper aged 4 cf, ab, af, cf, ab, af, 2.064 1.763 1.84 2.713 days1.79 1.885 Averaged fiber tear on Inland paper board (overnight) @ 5° C.(%) 94  88  5 3 89 — @ −12° C. (%) 46  60  62  13 99 — cf—cohesivefailure; af—adhesive failure; ab—adhesive break sf—substrate failure;ss—slip stick, 6+ - longer than 6 seconds

REXTAC RT 2715 is a copolymer of propylene, butene and ethylene havingabout 67.5 mole percent propylene, about 30.5 mole percent butene andabout 2 mole percent ethylene produced by Huntsman, Company. Thecopolymer has about 11 mole percent BB dyads, 40 mole percent PB dyadsand about 49 mole percent PP dyads. The melting point is 76° C. with amelting range form 23 to 124° C. the Tg is −22° C., the crystallinity isabout 7 percent, the enthalpy is 11 J/g by DSC. The Mn is 6630 the Mw is51200 and the Mz 166,700 by GPC. Mw/Mn is 7.7.

Adhesion tests on substrate fiber tear (Dot T-peel) Formulation HM7 HM8HM9 HM10 HM11 HM12 HM13 HM14 Polymer PP6 PP6 PP7 PP7 PP8 PP8 PP9 PP9Polymer (wt. %) 99 90.1 99 90.1 99 90.1 99 90.1 Escorez 5637 0 3 0 3 0 30 3 (wt. %) Irganox 1010 1 1 1 1 1 1 1 1 (wt. %) AC 1302P 0 6 0 6 0 6 06 (wt. %) Shore A 65 61 82 83 93 88 92 95 hardness Set time (sec) 3 2.56 1.5 4 1.5 3.5 1.5 Viscosity @ 190° C. 1193 1066 1027 927.5 1320 11301192 1027 (cps) SAFT (° F.) 229 229 250 249 264 263 >270 254 Paperboard84C 100 100 95 88 20 86 3 0 overnight (%) File folder 100 100 100 100100 100 100 100 overnight (%) Paperboard 84C 98/99 98/98 91/96 30/9997/96 93/98 69/89 77/95 overnight (%): 5° C./−12° C. File folder 100/98100/90 100/100 100/100 98/99 98/96 90/89 95/82 overnight (%): 5° C./−12°C.

Adhesion tests on substrate fiber tear and failure types (Dot T-peel)Formulation HM15 HM16 HM17 HM18 HM19 HM20 HM21 HM22 PP11 (wt. %) 77.577.5 77.5 77.5 77.5 79.6 81.6 C80 wax 8.2 8.2 8.2 8.2 8.2 8.5 8.7Escorez 5690 8.6 8.6 8.6 8.6 8.6 8.8 9.0 Irganox 1010 0.7 0.7 0.7 0.70.7 0.7 0.7 AC 596P (wt. %) 5 AC 597 (wt. %) 5 2.5 AC X1325 (wt. %) 5MAPP 40 (wt. %) 5 AC 1302P (wt. %) 5 Advantra 9250 100 (wt. %) Set time(sec) 2 2.5 3 2.5 2.5 2.5 3~3.5 1.5 Shore A hardness 73 71 76 71 68 6864 89 Substrate fiber tear at low temperatures (%) Paperboard 84C 100 98100 91 79 98 99 98 @ −10° C. Paperboard 84C 96 96 98 100 100 100 99 98 @−30° C. Inland Paper 93 96 90 89 0, ab, af 8 0, ab, af 90 Board @ −10°C. Inland Paper 10 91 37 90 40 24 0, ab, af 80 Board @ −30° C. Substratefiber tear at ambient condition Inland paper board 100 99 100 100 99 10099 98 Paperboard 84C 100 100 100 100 100 99 100 100 ab—adhesive break,af—adhesive failure

Adhesion tests of substrate fiber tear (Dot-T peel) Formulation HM23HM24 HM25 HM26 HM27 HM28 PP3 (wt. %) 100  82.2 81.3 77.2 73.6 70.3 PP1(wt. %) 0 0 0 0 4.7 9 Paraflint H-1 0 9.9 5.2 5 4.7 4.5 (wt. %) Escorez0 6.9 7.3 6.9 6.6 6.3 5637 (wt. %) Irganox 1010 0 1 1 1 1 0.9 (wt. %)PP-grafted 0 0 5.2 5 4.7 4.5 maleic anhydride (wt. %) Sigma- AldrichKaydol oil 0 0 0 5 4.7 4.5 (wt. %) Shore A 75  80 80 67 64 73 hardnessSet time  6+ 1 1.5 to 2 2 2.5 2.5 (sec) Viscosity @ 1040   763 772.5 681640 761.7 190° C. (cps) SAFT (° F.) — 233 — — — — Paperboard 67  0 100100 100 100 84C overnight (%) File folder 100  0 100 100 100 100overnight (%) Paperboard 50/ 0/0 90/95 98/98 98/99 100/ 84C 100overnight (%): 5° C./ −12° C. File folder 100/ 0/0 100/ 100/ 100/ 100/overnight 100 100 100 100 (%): 5° C./ −12° C.

Adhesion tests on substrate fiber tear (Dot-T peel) Formulation HM29HM30 HM31 HM32 HM33 HM34 HM35 HM36 HM37 HM38 PP2 71.6 67.2 74.8 70.382.2 77.2 78.3 73.6 74.8 70.3 PP1 8.6 8.6 4.5 4.5 5.0 5 9.4 9.4 9 9Paraflint H-1 4.3 4.3 4.5 4.5 5.0 5 4.7 4.7 4.5 4.5 (wt. %) Escorez 56376.0 6.0 6.3 6.3 6.9 6.9 6.6 6.6 6.3 6.3 (wt. %) Irganox 1010 0.9 0.9 0.90.9 1.0 1 0.9 0.9 0.9 0.9 (wt. %) MAPP 40 (wt. %) 0.0 4.3 0.0 4.5 0.0 50 4.7 0 4.5 Kaydol oil 8.6 8.6 9.0 9.0 0.0 0 0 0 4.5 4.5 (wt. %) Shore A65 65 67 77 84 84 80 83 72 77 hardness Set time (sec) 3 2.5 3 1.5 2 1.52.5 2 3 1.5 Viscosity @ 190° C. 344 332 332.5 401.6 460.2 477.5 488 528380 487.5 (cps) SAFT (F) — 263 — 263 — 270 — 270 — 268 Substrate fibertear (%) Paperboard 84C 3.4 100 0 100 0 100 30 100 0 100 overnight (%)File folder 70 100 65 100 90 100 60 100 60 100 overnight (%) Paperboard84B 100 100 100 100 100 100 100 100 100 100 overnight (%) Paperboard 84C0 100 0 100 0 100 0 100 0 100 overnight at 5° C. (%) File folder 0 10020 100 100 100 30 100 100 100 overnight @ 5° C. (%) Paperboard 84B 100100 67 100 100 100 100 100 100 100 overnight at 5° C. (%)

Adhesion tests of substrate fiber tear (Dot-T peel) Formulation HM39HM40 HM41 HM42 PP4 82.2 99  0 0 PP5 0 0 82.2 99  Paraflint H-1 (wt. %) 50 5 0 Escorez 5637 (wt. %) 6.9 0 7 0 Irganox 1010 (wt. %) 1 1 1 1 MAPP40 (wt. %) 5 0 5 0 Shore A hardness 85 82  88 88  Set time (see) 2  6+ 2 6+ Viscosity @ 190° C. (cps) 737.1 1070   937.5 1275   Paperboard 84Covernight (%) 100 0 100 0 File folder overnight (%) 0 100  100 100 Paperboard 84C overnight 83/100 63/95 98/95 80/100 (%): 5° C./−12° C.File folder overnight (%): 65/95  70/50 90/90 80/100 5° C./−12° C.

Adhesion tests of substrate fiber tear (Dot T-peel) Formulation HM43HM44 HM45 HM46 HM47 HM48 HM49 HM50 PP3 100  86.5 81.3 82.2 77.2 78.373.6 0 Paraflint H-1 0 5.2 5.2 5 5 4.7 4.7 0 (wt. %) Escorez 5637 0 7.37.3 6.9 6.9 6.6 6.6 0 (wt. %) Irganox 1010 0 1 1 1 1 0.9 0.9 0 (wt. %)MAPP 40 (wt. %) 0 0 5.2 0 5 0 4.7 0 Kaydol oil (wt. %) 0 0 0 4.95 5 9.49.4 0 Henkel hot melt 100 80-8368 (wt. %) Shore A hardness 75  72 72 6676 64 64 82 Set time (sec)  6+ 2 1.5 2 1.5 2.5 1.5 1 Viscosity @ 190° C.1040   — 765 — 731 — 508 717.5 (cps) SAFT (° F.) — — 268 — 268 — 263 177Paperboard 84C 67  100 100 34 100 34 100 100 overnight (%) File folder100  100 100 100 100 100 100 100 overnight (%) Paperboard 84B 100  100100 100 100 100 100 100 overnight (%) Paperboard 84C 50/ 60/ 94/100 34/97/97 24/ 100/67 100/100 overnight (%): 5° C./ −12° C. File folder 100/100/ 100/25 100/ 0/70 100/ 100/88 100/100 overnight (%): 5° C./ −12° C.

Adhesion tests of substrate fiber tear (Dot T-peel) Formulation HM51HM52 HM53 HM54 HM55 Polymer 80 75 75 75 75 PP12 (wt. %) Escorez 10 10 1010 10 5690 (wt. %) C80 Wax 10 10 10 10 10 (wt. %) Irganox 1010 0.7 0.70.7 0.7 0.7 (wt. %) Modifier — SP6-g-MA SP4-g-MA SP3-g-MA PP12-g-MAModifier — 5 5 5 5 (wt. %) Viscosity at 1650 3090 2350 1990 170° C.(cps) Set time 3 3.5 3.5 3 3.5 (sec) Shore A 83/63 86/67 81/68 85/6681/71 hardness Percent of fiber tear on Inland paperboard @ 25° C. 96100 99 98 94 @ −8° C. 0 58 43 18 43 @ −30° C. 13 75 48 1 68

Adhesion tests of substrate fiber tear (Dot T-peel) Formulation HM56HM57 HM58 HM59 HM60 HM61 HM62 HM63 Polymer PP12 80 75 75 75 77 75 75 75(wt. %) Escorez 5690 10 10 10 10 10 10 10 10 (wt. %) C80 Wax (wt. %) 1010 10 10 10 10 10 10 Irganox 1010 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 (wt.%) Modifier VM- VM- VM- VM- VM-3000- VM-2000- EP-3-g- 1000 3000 20002000 g-MA g-MA MA Modifier (wt. %) — 5 5 5 3 5 5 5 Viscosity at 16502020 2590 2700 1800 2120 2250 2040 170° C. (cps) Set time (sec) 3 4 3 44 3.5 2.5 4 Shore A 83/63 87/68 93/71 75/58 76/60 88/71 88/65 78/61hardness Percent of fiber tear on Inland paperboard at varioustemperatures @ 25° C. 96 99 95 98 99 99 99 99 @ −8° C. 0 0 55 38 0 3 6528 @ −30° C. 13 3 4 30 0 8 80 30

In the following examples, the olefin polymer of the present inventionare, labeled either as aPP-iPP's or POA's, and are propylenehomopolymers prepared with two metallocene catalysts as described above.As an example of the mixed catalyst systems for preparing this type ofpolymer, one catalyst,di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafniumdimethyl, produces atactic polypropylene, aPP whereas the secondcatalyst, rac-dimethylsilyl bis(2-methyl-4-phenylindenyl)zirconiumdimethyl, produces isotactic polypropylene, iPP.

In the examples, polymerization temperature was changed to vary themolecular weight of the polymer. Under some polymerization conditions,crosslinking of aPP and iPP polymer chains occurs so that a small amountof aPP-g-iPP is present. Several of these propylene-based polymers usedin this work are described in the table below, where η is the Brookfieldviscosity measured according to ASTM D3236. The heat of fusion (ΔHf)value of each polymer can be considered as a measure of crystallinity.The heat of fusion for crystalline PP is 207 J/g. The heat of fusionvalue of each aPP-iPP in the table below divided by 207 J/g is thedegree of crystallinity. Therefore, aPP-iPP-1, -2 and -3 have similardegrees of crystallinity, whereas aPP-iPP-4, -5 and -6 are lesscrystalline. The g_(w)′ is the weight-average branching coefficient. Alower g_(w)′ suggests a higher concentration and/or higher level ofaPP-g-iPP in the aPP-iPP polymer.

Functionalized srPPs

Syndiotactic rich polymers were produced according to the generalprocedures described above. The catalysts used wasdiphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl, theactivator used wasN,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate. Thepolymerization for srPP-1 was 110° C., and for srPP2 was run at 120° C.,both in hexane. The polymers have % [r] dyads ˜58-75. Each srPP polymerhas very low degree of crystallinity and is almost amorphous.

The functionalized srPP's used in this study are shown the table belowwhere srPP-i represents the precursor polymer of the MA-srPP-i,Amide-srPP-i or Acid-srPP-i. It is interesting to note that, afterfunctionalization, molecular weights were decreased in all cases. Tocompare the performance of functionalized srPP-1′ s to theirnon-functionalized counterparts, the lowest molecular weight srPP-3polymer was used as a control. Even though srPP-3 has molecular weights(M_(n), M_(n) and M_(z)) approximately two times higher than thefunctionalized srPP-1's, we choose srPP-3 as the control because itsmolecular weights are closer to the functionalized components.

In an example, functionalization of the polymers was carried out bydissolving 120 g of polymer in toluene (polymer concentration: 20 wt %).Fifteen wt % maleic anhydride based on srPP was used. The radicalinitiator, 2,5-dimethyl-2,5-di(t-butylperoxyl)hexane, was 2.5 wt % basedon srPP. The reaction temperature was 139° C. and the reaction time was4 hr.

POLYLETS® MAPP 40, available from CHUSEI, are shown below. Thiscommercially available MAPP-40 has a higher MA content but a higherdegree of crystallinity than the MA-srPP polymers used in this study.

Characterization of Propylene-Based Polymers. aPP-iPP- 1 2 3 4 5 6Catalyst #1 B B B B B B Catalyst #2 D D D D D D T_(c), ° C. 88 90 92 8078 68 T_(m), ° C. 127 138 141 139 132 136 T_(g), ° C. −6 −5 −4 −6ΔH_(u), J/g 37 38 38 32 29 22 Viscosity at 1900 4000 11000 2400 16001500 190° C. η, cp M_(n)/1000 13.0 15.2 20.4 19.6 13.1 M_(w)/1000 37.645.2 55.0 41.1 29.3 M_(z)/1000 64.0 81.0 94.6 76.0 62.6 g′_(w) 0.93 0.950.93 0.88 0.99

Characterization of srPP's. Rxn Temp., M_(n)/ M_(w)/ M_(z)/ Wt % Polymer° C. Catalyst 10³ 10³ 10³ g′_(w) FG* srPP-1 110 E4 23 62 148 1.08 0srPP-3 120 E4 17 43 80 0.98 0 srPP-4 107 E4 34 86 177 1.05 0 srPP-5 94E4 74 188 385 1.11 0 srPP-6 90 ED4 128 311 606 1.19 0 srPP-1-g-MA 8 2038 3.20 srPP-3-g-MA 17 33 55 1.92 srPP-4-g-MA 23 44 71 1.00 srPP-5-g-MA29 68 116 1.00 srPP-6-g-MA 60 135 263 1.12 srPP-1-g-amide ~8 ~20 ~38~1.00 srPP-1-g-acid ~8 ~20 ~38 ~1.00 MAPP-40 3.7 9.8 18 5.24 *FunctionalGroup E4 is a combination ofdiphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethyl andN,N-dimehtyl aniliniumtetrkis(pentafluorphenyl) borate

Molecular Weight Change of srPP After Maleation. Polymer T_(rxn), ° C.Catalyst M_(n)/10³ M_(w)/10³ M_(z)/10³ M_(w)/M_(n) ΔM_(w)/M_(w) g′_(w)Wt % MA srPP-3 120 E4 17 43 80 2.53 0.98 0 srPP-3-g-MA 17 33 55 1.940.23 1.92 srPP-4 107 E4 34 86 177 2.53 1.05 0 srPP-4-g-MA 23 44 71 1.910.49 1.00 srPP-5 94 E4 74 188 385 2.54 1.11 0 srPP-5-g-MA 29 68 116 2.340.64 1.00 srPP-6 90 E4 128 311 606 2.43 1.19 0 srPP-6-g-MA 60 135 2632.25 0.57 1.12

Adhesion to Mylar for Compositions without Tackifier. T-Peel, lb/inFailure Mode aPP-iPP-1 0.03 AF aPP-iPP-1 + 20 Wt % srPP-3 0.10 AFaPP-iPP-1 + 20 Wt % MAPP-40 0.19 CF aPP-iPP-1 + 20 Wt % srPP-1-g-amide0.10 AF aPP-iPP-1 + 20 Wt % srPP-1-g-MA 0.48 AF aPP-iPP-2 0.03 ≡ P₁AF/CF aPP-iPP-2 + 20 Wt % srPP-3 0.04 AF aPP-iPP-2 + 20 Wt % MAPP-400.20 CF aPP-iPP-2 + 20 Wt % srPP-1-g-acid 0.05 AF aPP-iPP-2 + 20 Wt %srPP-1-g-amide 0.08 CF aPP-iPP-2 + 20 Wt % srPP-1-g-MA 1.21~40P₁ AFaPP-iPP-2 + 20 Wt % srPP-3-g-MA 1.83 CF/AF aPP-iPP-2 + 20 Wt %srPP-4-g-MA 2.12 AF aPP-iPP-2 + 20 Wt % srPP-5-g-MA 6.28~200P₁ CF/AFaPP-iPP-2 + 20 Wt % srPP-6-g-MA 4.58 AF aPP-iPP-3  0.001 AF aPP-iPP-3 +20 Wt % srPP-3 0.02 AF aPP-iPP-3 + 20 Wt % MAPP-40 0.32 CF aPP-iPP-3 +20 Wt % srPP-1-g-amide 0.09 AF aPP-iPP-3 + 20 Wt % srPP-1-g-MA 0.40 AF

Adhesion to Mylar for Compositions with Tackifier(aPP-iPP/E-5380/Polymer Modifier = 72/8/20 Wt. Ratio) T-Peel,lb/inFailure Mode aPP-iPP-2/E-5380 (9 to 1 Wt. Ratio) 0.04 ≡ P₂ AFaPP-iPP-2/E-5380/srPP-3 0.04 AF aPP-iPP-2/E-5380/MAPP-40 0.14 CFaPP-iPP-2/E-5380/srPP-1-g-acid 0.06 AF aPP-iPP-2/E-5380/srPP-1-g-amide0.22 AF aPP-iPP-2/E-5380/srPP-1-g-MA 2.15~50 P₂ CF/AFaPP-iPP-2/E-5380/srPP-3-g-MA 2.56 CF aPP-iPP-2/E-5380/srPP-4 0.05 AFaPP-iPP-2/E-5380/srPP-4-g-MA 5.83 CF aPP-iPP-2/E-5380/srPP-5 0.13 AFaPP-iPP-2/E-5380/srPP-5-g-MA 12.02  AF/CF aPP-iPP-2/E-5380/srPP-6 0.02AF aPP-iPP-2/E-5380/srPP-6-g-MA 13.77~350 P₂ CF E-5380 is ESCOREZ 5380 ™a hydrogenated dicyclopentadien based hydrocarbon resin having a Ringand Ball softening point of about 85° C. available form ExxonMobilChemical Co. ion Houston Texas.

Bonding to Mylar and iPP of Modified POA's. T-Peel to Failure T-Peel toFailure Mylar, lb/in Mode iPP, lb/in Mode aPP-iPP-2/MAPP-40 0.20 CF 2.90CF aPP-iPP-2/E-5380/ 0.14 CF 2.87 CF MAPP-40 aPP-iPP-2/E-5380 0.04 AF3.09 CF aPP-iPP-2/E-5380/srPP-3 0.09 AF >10.31 Substrate BrokenaPP-iPP-2/E-5380/SrPP- 2.15 CF/AF >8.53 Substrate 1-g-MA Broken

Bonding to Mylar and iPP of MAPP-40 and MA-srPP's. T-Peel to FailureT-Peel to Failure Mylar, lb/in Mode iPP, lb/in Mode MAPP-40 0.005 AF3.65 CF MA-srPP-3 6.60 CF 5.72 CF SrPP-4-g-MA 8.13 CF 7.80 CF MA-srPP-51.66 AF 11.17 CF SrPP-6-g-MA 2.59 AF >5.96 Substrate Broken

POA's Modified by Tackifier and Wax. Formulated PP-1 Formulated PP-2aPP-iPP-4 79.4 — aPP-iPP-5 — 81.6 E-2203 (T_(g) = 47° C.) 13.4 — E-5690(T_(g) = 45° C.) — 9.02 Paraflint C80 6.7 8.68 Irganox 1010 0.50 0.69T-Peel to Mylar, lb/in 0.23 0.45 Failure Mode AF CF

Adhesion to Mylar for Compositions Based on aPP-iPP-6(aPP-iPP/E-5380/Polymer Modifier = 72/8/20 Wt. Ratio) T-Peel, ib/inFailure Mode aPP-iPP-6 0.07 CF aPP-iPP-6/E-5380 (9 to 1 Wt. Ratio) 0.19CF aPP-iPP-6/E-5380/SrPP-3-g-MA 4.32 CF aPP-iPP-6/E-5380/SrPP-4-g-MA6.94 CF aPP-iPP-6/E-5380/SrPP-5-g-MA 11.1 CF aPP-iPP-6/E-5380/MA-srPP-612.0 CF

The blends of the olefin polymer with each functionalized component weremixed thoroughly and homogeneously in the thermal cell of a Brookfieldviscometer equipped with an electrically driven stirrer at 180° C. Aftermix, the blends were degassed in a vacuum oven (continuously purged bynitrogen) at 180° C. and subsequently cooled down to 25° C. Eachadhesive sample composition was then molded into a thin sheet ofmaterial with thickness about 0.4 mm using a molding temperature of 180°C. and a molding time of 10 seconds. For the preparation of the T-peelspecimens, this thin sheet of adhesive sample was laminated between twopieces of Mylar substrate (3-mil thickness) in a positive pressure,Teflon-coated mold. The bonding temperature was 180° C. and the bondingtime was 10 seconds. The laminate was then cut into ½″=1.3 cm widespecimens. All the T-peel measurements were performed at roomtemperature and at a separation speed of 2 inches per minute=850micrometers per second (μm/s).

As the data shows, the functionalized srPP provide a benefit to theT-peel strengths to Mylar of these compositions. Clearly, functionalgroups improve adhesion of propylene-based polymer to Mylar with the MAgroup showing the better results. Also, viscosity (or molecular weight)of the propylene-based polymer will affect adhesion, with the mediummolecular weight polymer.

As the examples also show, the compositions of the present inventionprovide enhanced adhesion to both polar and non-polar substrates. Theycan be applied to various areas, such as adhesives, tie layers, and thelike. The examples are directed to the bonding of paper cardboard forpackaging hot melt adhesive (HMA) applications. As above, the inventiveformulations were prepared by blending component 1, the aPP-iPP polymerand a functionalized polyolefin (such as MA-srPP with other ingredients,such as tackifier, wax, antioxidant, plasticizer oil, liquid resintackifier, and the like) under low or high shear mixing at elevatedtemperatures to form a fluid melt. Mixing temperatures varied from about130° C. to about 190° C.

1. An adhesive comprising: i) at least one functionalized componentchosen from functionalized polymers, functionalized oligomers and betanucleating agents; and ii) an olefin polymer comprising 50 wt % or moreof an alpha-olefin having 3 to 30 carbon atoms, where the olefin polymerhas a Dot T-Peel of 1 N or more on Kraft paper, an Mw of 10,000 to100,000, a g′ measured at the Mz of 0.95 or less, a heat of fusion of 1to 70 J/g, a heptane insoluble fraction of 70 wt % or less, based uponthe weight of the starting olefin polymer.
 2. The adhesive of claim 1,wherein the heptane insoluble fraction has a branching index g′ of 0.9or less as measured at the Mz of the polymer.
 3. The adhesive of claim1, wherein the heptane insoluble fraction has a branching index g′ of0.7 or less as measured at the Mz of the polymer.
 4. The adhesive ofclaim 1, wherein the olefin polymer has a percent crystallinity ofbetween 5 and 40% or less.
 5. The adhesive of claim 1, wherein theolefin polymer has heat of fusion of from 20 to 70 J/g.
 6. The adhesiveof claim 1, wherein the olefin polymer has heat of fusion of from 30 to60 J/g.
 7. The adhesive of claim 1, wherein the olefin polymer has apercent crystallinity of 10-30%.
 8. The adhesive of claim 1, wherein theolefin polymer has tensile strength at break of 0.75 MPa or more.
 9. Theadhesive of claim 1, wherein the olefin polymer has a Dot T-Peel ofbetween 3 and 10,000 N.
 10. The adhesive of claim 1, wherein the olefinpolymer has a Tg of between 5 and −65° C.
 11. The adhesive of claim 1,wherein the olefin polymer comprises at least 50 wt % propylene and upto 50 wt % of a comonomer chosen from butene and hexene.
 12. Theadhesive of claim 1, wherein tackifier is present at 1 to 60 wt %. 13.The adhesive of claim 1, wherein the olefin polymer has a Tg of 0° C. orless.
 14. The adhesive of claim 1, wherein the olefin polymer has a meltindex of 50 dg/min or more.
 15. The adhesive of claim 1, wherein thefunctionalized component is present at 0.1 to 10 wt %.
 16. The adhesiveof claim 1, wherein the functionalized component comprisesfunctionalized polymer.
 17. The adhesive of claim 1, wherein thefunctionalized component comprises functionalized polymer selected fromthe group consisting of maleated polyethylene, maleated metallocenepolyethylene, maleated metallocene polypropylene, maleated ethylenepropylene rubber, and functionalized polyisobutylene.
 18. The adhesiveof claim 1, wherein the functionalized component comprisesfunctionalized oligomer.
 19. The adhesive of claim 1, wherein thefunctional component comprises a functional group selected from thegroup consisting of maleic anhydride, citraconic anhydride, 2-methylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleicanhydride, bicyclo [2,2,1]-5-heptene-2,3-dicarboxylic anhydride and4-methyl-4-cyclohexene-1,2dicarboxylic anhydride, acrylic acid,methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconicacid, mesaconic acid, crotonic acid,bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,&g,lo-octahydronaphthalene-2,3-dicarboxylic acid anhydride,2-oxa-1,3-diketospiro (4.4)non-7-ene, bicyclo (2.2.1)hept- 5- ene-2,3-dicarboxylic acid anhydride, maleopimaric acid, tetrahydrophtalicanhydride, norborn-5-ene-2,3-dicarboxylic acid anhydride, nadicanhydride, methyl nadic anhydride, himic anhydride, methyl himicanhydride, and x -methyl-bicyclo(2.2.1)hept-5-ene-2,3- dicarboxylic acidanhydride (XMNA).
 20. The adhesive of claim 1, wherein the functionalcomponent comprises a functional polymer where the polymer of thefunctional polymer is polypropylene having a weight average molecularweight of 15,000 or less and a crystallinity of 5% or more.